U.S. patent number 6,630,430 [Application Number 09/616,568] was granted by the patent office on 2003-10-07 for fuel and oil detergents.
This patent grant is currently assigned to Huntsman Petrochemical Corporation. Invention is credited to Prakasa R. Anantaneni, George A. Smith.
United States Patent |
6,630,430 |
Anantaneni , et al. |
October 7, 2003 |
Fuel and oil detergents
Abstract
This invention is directed to lubricating compositions which
contain detergent components derived from linear alkylbenzenes
including sulfonates and salts and esters thereof. Detergents
provided by the invention have a higher content of the 2-phenyl
alkylbenzene isomers than was previously available in materials of
prior art. The detergents of the present invention are more
powerful detergents over those previously available and may be
employed as additives in various lubricating compositions,
including motor oils, cutting fluids, emulsions, and motor
fuels.
Inventors: |
Anantaneni; Prakasa R. (Austin,
TX), Smith; George A. (Austin, TX) |
Assignee: |
Huntsman Petrochemical
Corporation (Austin, TX)
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Family
ID: |
28679199 |
Appl.
No.: |
09/616,568 |
Filed: |
July 14, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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559841 |
Apr 26, 2000 |
6562776 |
|
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598692 |
Feb 8, 1996 |
5847254 |
|
|
|
174891 |
Oct 19, 1998 |
6133492 |
|
|
|
879745 |
Jun 20, 1997 |
6315964 |
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598695 |
Feb 8, 1996 |
5770782 |
|
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Current U.S.
Class: |
508/413; 184/1.5;
252/70; 508/389; 508/390; 508/391 |
Current CPC
Class: |
B01D
3/322 (20130101); B01J 27/12 (20130101); B01J
29/18 (20130101); B01J 37/26 (20130101); C01B
39/026 (20130101); C07C 2/66 (20130101); C07C
15/107 (20130101); C11D 1/22 (20130101); C07C
2/66 (20130101); C07C 15/107 (20130101); B01J
2229/16 (20130101); C07C 2521/12 (20130101); C07C
2521/16 (20130101); C07C 2527/126 (20130101); C07C
2529/16 (20130101); C07C 2529/18 (20130101); C07C
2529/70 (20130101) |
Current International
Class: |
B01J
27/06 (20060101); B01J 27/12 (20060101); B01J
29/00 (20060101); B01J 29/18 (20060101); B01D
3/14 (20060101); B01D 3/32 (20060101); B01J
37/26 (20060101); B01J 37/00 (20060101); C07C
2/66 (20060101); C01B 39/00 (20060101); C01B
39/02 (20060101); C07C 15/00 (20060101); C07C
15/107 (20060101); C07C 2/00 (20060101); C11D
1/22 (20060101); C11D 17/00 (20060101); C11D
1/02 (20060101); C10M 000/00 () |
Field of
Search: |
;508/413,389,390,391
;184/1.5 ;252/70 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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353 813 |
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Feb 1990 |
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EP |
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WO 99/05243 |
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Feb 1999 |
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WO |
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WO 00/23548 |
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Apr 2000 |
|
WO |
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WO 00/23549 |
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Apr 2000 |
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WO |
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Other References
"Linear Alkylbenzene" by DeAlmeida et al. JAOCS, vol. 71, No. 7
(Jul., 1994)..
|
Primary Examiner: Gupta; Yogendra N.
Assistant Examiner: Hamlin; D. G.
Attorney, Agent or Firm: Whewell; Christopher J.
Parent Case Text
This application is a continuation-in-part application of
application Ser. Nos.: 09/559,841 filed Apr. 26, 2000 U.S. Pat. No.
6,562,776; 08/598,692, filed Feb. 8, 1996 U.S. Pat. No. 5,847,254;
and 09/174,891 filed Oct. 19, 1998 U.S. Pat. No. 6,133,492 and of
application Ser. No. 08/879,745, filed Jun. 20, 1997 U.S. Pat. No.
6,315,964 which is a divisional of Ser. No. 08/598,695, filed Feb.
8, 1996, now U.S. Pat. No. 5,770,782, the contents of which are
expressly incorporated herein by reference. This Application claims
the benefit of U. S. Provisional Application No. 60/178,823 filed
Jan. 28, 2000, which is currently still pending.
Claims
What is claimed is:
1. A composition useful as a lubricant that is formed from
components comprising: a) a base oil; and b) an effective detergent
amount of an alkylbenzene surfactant component, said component
characterized as comprising any amount between 35.00% and 82.00% by
weight based upon the total weight of the component, including
every hundredth percentage therebetween, of derivatives of the
2-phenyl isomers of alkylbenzenes described by the general formula:
##STR4##
in which n may be any integer between 13 and 27, and in which
R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each
independently selected from the group consisting of: hydrogen, a
methyl group, an ethyl group, a propyl group, a butyl group, a
sulfonic acid group, a sulfonate group, and a sulfonate ester
group.
2. A composition according to claim 1 wherein R.sub.2 and R.sub.3
are each independently selected from the group consisting of
hydrogen and a sulfonate group, R.sub.1 and R.sub.5 are hydrogen,
and R.sub.4 is selected from hydrogen, a methyl group, or an ethyl
group.
3. A composition according to claim 1 wherein R.sub.2 is sulfonate,
R.sub.3 is methyl, R.sub.1 and R.sub.5 are hydrogen, and R.sub.4 is
selected from the group consisting of: hydrogen, a methyl group, or
an ethyl group.
4. A composition according to claim 1 wherein R.sub.2, R.sub.3, and
R.sub.4 are each independently selected from the group consisting
of hydrogen and a sulfonate group, and R.sub.1, R.sub.5 are each
independently selected from the group consisting of hydrogen, a
methyl group, or an ethyl group.
5. A composition as in claim 1 in which R.sub.1 R.sub.2, and
R.sub.5 are hydrogen, R.sub.3 is selected from the group consisting
of a methyl group or an ethyl group, and R.sub.4 is a sulfonic acid
group.
6. A composition as in claim 1 in which R.sub.1, R.sub.2, and
R.sub.4 are hydrogen, R.sub.3 is selected from the group consisting
of a methyl group or an ethyl group, and R.sub.5 is a sulfonic acid
group.
7. A composition as in claim 1 in which R.sub.1, R.sub.2, and
R.sub.4 are hydrogen, R.sub.1 is selected from the group consisting
of a methyl group or an ethyl group, and R.sub.3 is a sulfonic acid
group.
8. A composition as in claim 1 in which R.sub.1, R.sub.3, and
R.sub.4 are hydrogen, R.sub.5 is selected from the group consisting
of a methyl group or an ethyl group, and R.sub.2 is a sulfonic acid
group.
9. A composition according to claim 1 in which R.sub.2 and R.sub.5
are both methyl and R.sub.1, R.sub.3, and R.sub.4 are each
independently selected from the group consisting of hydrogen or a
sulfonate group.
10. A composition according to claim 1 in which R.sub.4 and R.sub.5
are both methyl and R.sub.1, R.sub.2, and R.sub.3 are each
independently selected from the group consisting of hydrogen or a
sulfonate group.
11. A composition according to claim 1 in which R.sub.3 and R.sub.4
are both methyl and R.sub.1, R.sub.2, and R.sub.5 are each
independently selected from the group consisting of hydrogen or a
sulfonate group.
12. A composition according to claim 1 wherein the predominant
amount of said derivatives are those in which only one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 is a sulfonate group, and in
which said derivatives are sulfonate salts of metals selected from
the group consisting of: alkali metals or alkaline earth
metals.
13. A composition according to claim 12 wherein said salts are
salts of metals selected from the group consisting of:sodium,
potassium, lithium, calcium, magnesium, strontium and barium.
14. A composition according to claim 1 further comprising a
material selected from the group consisting of:
corrosion-inhibiting agent, detergent, dispersant, antioxidant,
viscosity improving agent, antiwear agent, extreme-pressure agent,
pour-point depressant, friction-modifier, fluidity-modifier,
anti-foam agent, or mixture of two or more thereof.
15. A composition according to claim 1 further comprising any
amount between 0.01% and 20.00% by weight based upon the total
weight of the composition of a component that comprises at least
one other component known to be useful in formulating lubricants,
oils, cutting fluids and the like, wherein at least one of said
other components is selected from the group consisting of:
anti-oxidants, friction modifiers, pour point depressants,
viscosity index improvers, extreme pressure additives, sulfurized
olefins, water, aromatic hydrocarbons, aliphatic hydrocarbons,
anti-foam agents, a hydrocarbon-based oil, a vegetable oil, a
metallic dithiophosphate, an overbased sulfonate, a dye, a
hydrocarbon-soluble ashless dispersant, an alkali metal or alkaline
earth metal salt of a sulfonic acid, an alkali metal or alkaline
earth metal salt of a fatty acid and alkylbenzene sulfonates having
a 2-phenyl isomer content of less than 50.00%.
16. A composition according to claim 1 wherein the 2-phenyl isomers
content of the alkylbenzene surfactant component comprises any
amount between 45.00% and 82.00% by weight based upon the total
weight of the component, including every hundredth percentage
therebetween.
17. A composition according to claim 1 wherein the 2-phenyl isomers
content of the alkylbenzene surfactant component comprises any
amount between 57.00% and 82.00% by weight based upon the total
weight of the component, including every hundredth percentage
therebetween.
18. A composition according to claim 1 wherein said alkylbenzene
surfactant component is present in any amount between 0.03% and
49.95% by weight based upon the total weight of said composition
useful as a lubricant.
19. A composition as in claim 1 wherein the alkylbenzene surfactant
component comprises only one alkyl group bonded to a benzene ring,
and wherein none of R.sub.1, R.sub.2, R.sub.3, R.sub.4, or R.sub.5
are hydrocarbyl.
20. A composition as in claim 19 wherein the alkyl group is
substantially linear.
21. A composition as in claim 19 wherein the alkyl group is a
branched alkyl group.
22. A composition according to claim 14 wherein said material is
present in any amount between 0.10% and 25.00% by weight based upon
the total weight of said composition useful as a lubricant.
23. A composition according to claim 14 wherein said material is a
mixture of branched alkylbenzene sulfonates wherein said branched
alkylbenzene sulfonates comprise one branched alkyl group bonded to
a benzene ring, and wherein said alkyl group comprises any integral
number of carbon atoms between 16 and 30.
24. A composition useful as a lubricant that is formed from
components comprising: a) an alkylbenzene surfactant component
present in any amount between 0.01% and 50.0% by weight based upon
the total weight of the composition, said component characterized
as comprising any amount between 37.00% and 82.00% by weight based
upon the total weight of the component, including every hundredth
percentage therebetween, of derivatives of the 2-phenyl isomers of
alkylbenzenes described by the general formula: ##STR5## wherein n
is equal to any integer between 13 and 27, and in which R.sub.1,
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently
selected from the group consisting of: hydrogen, a methyl group, an
ethyl group, a propyl group, a butyl group, a sulfonic acid group,
a sulfonate group, and a sulfonate ester group; and b) at least
50.0% by weight of a base oil.
25. A composition useful as a fuel for an internal combustion
engine that is formed from components comprising: a) a motor fuel;
and b) an effective detergent amount of an alkylbenzene surfactant
component, said component characterized as comprising any amount
between 35.00% and 82.00% by weight based upon the total weight of
the component, including every hundredth percentage therebetween,
of derivatives of the 2-phenyl isomers of alkylbenzenes described
by the general formula: ##STR6## wherein n is equal to any integer
between 13 and 27, and in which R.sub.1, R.sub.2, R.sub.3, R.sub.4,
and R.sub.5 are each independently selected from the group
consisting of: hydrogen, a methyl group, an ethyl group, a propyl
group, a butyl group, a sulfonic acid group, a sulfonate group, and
a sulfonate ester group.
26. A composition according to claim 25 further comprising a base
oil present in an amount sufficient to effect lubrication of fuel
injectors.
27. A composition according to claim 25 in which said derivatives
are sulfonate salts of metals selected from the group consisting
of: alkali metals or alkaline earth metals, and wherein at least
51% by weight of said derivatives are those in which only one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 is a sulfonate
group.
28. A composition according to claim 27 wherein said salts include
are selected from the group of: sodium, potassium, lithium,
calcium, magnesium, strontium, barium, and ammonium salts.
29. A composition according to claim 28 wherein the derivatives are
ammonium salts and said ammonium salts include at least one
ammonium salt capable of functioning as an ashless dispersant in a
fuel composition useful in internal combustion engines.
30. A composition of matter that comprises: a) a cationic portion
comprising a hydrocarbon soluble ashless dispersant; and b) an
anionic portion comprising an alkylbenzene sulfonate surfactant
component, said alkylbenzene sulfonate surfactant component
characterized as comprising any amount between 35.00% and 82.00% by
weight based upon the total weight of the alkylbenzene sulfonate
surfactant component, including every hundredth percentage
therebetween, of sulfonates of the 2-phenyl isomers of
alkylbenzenes described by the general formula: ##STR7## wherein n
is equal to any integer between 13 and 27, and in which R.sub.1,
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently
selected from the group consisting of: hydrogen, a methyl group, an
ethyl group, a propyl group, a butyl group, a sulfonic acid group,
or a sulfonate group, or a sulfonate ester group, with the proviso
that only one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 is
a sulfonate group.
31. A composition of matter comprising: a) a minor amount of a
composition according to claim 30; and b) a major amount of a
material selected from the group consisting of: a motor fuel,
hydrocarbon diluent, or a base oil.
32. A concentrate which comprises: a) an alkylbenzene surfactant
component, said component characterized as comprising any amount
between 35.00% and 82.00 % by weight based upon the total weight of
the component, including every hundredth percentage therebetween,
of derivatives of the 2-phenyl isomers of alkylbenzenes described
by the general formula: ##STR8## wherein n is equal to any integer
between 13 and 27, and in which R.sub.1, R.sub.2, R.sub.3, R.sub.4,
and R.sub.5 are each independently selected from the group
consisting of: hydrogen, a methyl group, an ethyl group, a propyl
group, a butyl group, a sulfonic acid group, a sulfonate group, and
a sulfonate ester group; and b) a hydrocarbon diluent.
33. A composition of matter according to claim 32 further
comprising a base oil.
34. An mixture from which surfactants, lubricants, and motor fuels
may be produced, said mixture characterized as comprising any
amount between 35.00% and 82.00% by weight based upon its total
weight, including every hundredth percentage therebetween, of the
2-phenyl isomers of alkylbenzenes described by the general formula:
##STR9##
in which n is equal to any integer between 13 and 27, and in which
R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each
independently selected from the group consisting of: hydrogen, a
methyl group, an ethyl group, a propyl group, a butyl group, a
sulfonic acid group, a sulfonate group, and a sulfonic ester group,
wherein the dialkylbenzene content of the mixture is less than
1.0%, and wherein the viscosity of the alkylbenzene mixture is less
than 140 SUS units@ 37.8 degrees centigrade.
35. A mixture according to claim 34 wherein the viscosity of the
mixture is less than 120 SUS units@37.8 degrees centigrade.
36. A mixture according to claim 34 wherein the viscosity of the
alkylbenzene mixture is less than 100 SUS units@37.8 degrees
centigrade.
37. A mixture according to claim 34, wherein said derivatives
include a sulfonic ester group appended to the benzene ring.
38. A mixture according to claim 37 wherein the alcohol portion of
the ester from which said sulfonic ester group is derived comprises
a C.sub.1 to C.sub.25 hydrocarbon chain, whether linear alkyl or
branched alkyl.
39. The process of providing a metal surface with a lubricating
film comprising the step of contacting a composition according to
claim 1 to said metal surface.
40. The process of operating an internal combustion engine which
comprises the step of introducing a composition according to claim
25 into a combustion chamber and igniting the fuel.
Description
This invention relates to a oil-soluble compositions of matter
useful as detergent components in hydrocarbon oils useful for a
wide range of purposes, including without limitation general
lubricants, lubricating oils for internal combustion engines,
cutting fluids, emulsions, and dispersions.
More particularly, the invention relates to oil-soluble linear
alkylbenzenes comprising alkyl chains having between about 18 and
30 carbon atoms in which the alkylbenzenes have a low dialkylate
content and unique isomer distribution, including their sulfonate
and other water soluble and solubilizable derivatives.
BACKGROUND
The chemical structure and use of linear alkylbenzenes and their
derivatives, including their sulfonate derivatives, in the
manufacture of detergents is well known. Generally, linear
alkylbenzenes are produced by an alkylation reaction (according to
one of any well known processes for producing such materials) in
which the net result is the appendage of a hydrocarbyl radical to a
benzene ring. The source of the hydrocarbyl radical may be a
branched or a linear olefin, either an internal olefin or an alpha
olefin, and in practice a mixture of linear olefins is typically
used, which mixture comprises various olefins having different
numbers of carbon atoms per molecule. For the manufacture of
detergents, the range of carbon numbers (the number of carbon atoms
per molecule of an olefin used) of an olefin mixture used in the
alkylation reaction is typically in the range of between about 8
and 15 (inclusive) carbon atoms per molecule, which molecules are
sometimes collectively referred to by those in the art as the
"detergent range".
Alkylation of benzene using olefins in the detergent range leads to
a reaction product mixture which contains alkylated benzenes having
hydrocarbyl radicals of different chain length appended to a
benzene ring, and also contains position isomers of these
alkylation products. Thus, a reaction mixture from the alkylation
of benzene using detergent range olefins is often complex in
makeup.
Of the possible position isomers referred to above, it has been
recently discovered that detergents prepared from alkylbenzenes
having the benzene ring located at the 2-position on the
hydrocarbyl radical possess enhanced detergency and other
beneficial properties over the other isomers produced in the
alkylation. This is believed in part to be true because the
hydrocarbon chain that is appended to the ring extends a greater
distance in space in isomers having a phenyl group in the
2-position than the other position isomers, thus providing a
molecule having a more volumetrically exposed hydrocarbon chain
portion over other position isomers. Among other things, this
increased exposure provides increased availability for interaction
with hydrophobic materials which are sought to be solubilized in an
aqueous medium, when the alkylbenzene also includes a hydrophilic
moiety, such as a sulfonate group bonded to the benzene ring.
Surprisingly, more than one source of information in the prior art
mentions that a high 2-phenyl isomer content in
alkylbenzenes-derived detergent materials is undesirable. For
example, U.S. Pat. No. 3,342,888 mentions at column 2, line 37 et
seq. that a high 2-phenyl isomer content is associated with poor
sudsing characteristics. U.S. Pat. No. 3,387,056 mentions at column
2, lines 21-24 that a lower 2-phenyl isomer content improves the
product. U.S. Pat. No. 3,509,225 mentions at column 1, lines 59-62
that the 2-phenyl isomer is objectionable for use in commercial
detergent products because of its relatively low water solubility.
However, quite the opposite has been found to be true for the
compositions according to this invention, and it has now been
deemed desirable to provide alkylbenzenes having extremely high
amounts of the 2-phenyl isomer alkylation reaction products.
Detergents useful as components in hydrocarbon oils are often
possessive in general of the same properties as detergents useful
in aqueous media, that is, their molecules contain both a
hydrophilic and a hydrophobic portion. However, in many
applications it may be beneficial to employ alkylbenzenes having
longer hydrocarbon chains on the benzene ring than those found in
conventional detergents, for example to enhance solubility in
hydrocarbon oils, or to provide increased compatibility and
chemical inertness with respect to other components of the
formulation, depending upon the intended use. The production of
sulfonates by reaction with, e.g., SO.sub.3, is well known to those
skilled in the art. See, for example, the article "Sulfonates" in
Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition,
Vol. 19, pp. 291 et seq. published by John Wiley & Sons, N.Y.
(1969). Other descriptions of neutral and basic sulfonate salts and
techniques for making them can be found in the following U.S. Pat.
Nos. 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800;
2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,223,676; 2,239,974;
2,263,312; 2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022;
2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,347,568; 2,366,027;
2,374,193; 2,383,319; 3; 312,618; 3,471,403; 3,488,284; 3,595,790;
and 3,798,012. These and all other patents, books, excerpts,
articles, and literature cited herein are hereby incorporated by
reference for their disclosures.
Although the prior art is replete with prior art concerning the use
of alkylbenzene based detergents in hydrocarbon based oils such as
motor oils, hydraulic fluids, cutting fluids, etc., none have thus
far provided commercially quantities of an alkylbenzene based
detergent component in which the hydrocarbon tails of the molecule
have carbon numbers of any integral value in the range of between
about 16 and 30 carbon atoms per molecule, in which the 2-phenyl
isomer content is greater than about 50%, at prices low enough to
render such materials economically viable from the end user
perspective. Thus I have recognized that a need exists for a method
of linear alkylbenzene ("LAB") production having high substrate
olefin conversion, high selectivity to 2-phenyl isomer LAB, and
employing a catalyst having long lifetimes and easy handling, by
which high 2-phenyl isomer content and low dialkylate content can
be achieved in materials having relatively long hydrocarbon tails
attached to a benzene ring in a linear alkylbenzene based
detergent.
The present invention employs a mordenite catalyst in the
production of long-tail linear alkylbenzenes. The particular
mordenites useful in this invention may in one form of the
invention be mixed with a different catalyst that does not afford
high 2-phenyl isomer LAB production, to provide essentially any
desired percentage content of 2-phenyl isomer in the range of about
20-82% (on a weight basis) in the finished product by adjusting the
amounts of each catalyst. In this way, LAB may be produced having a
higher 2-phenyl isomer content than would be produced using the
non-mordenite catalyst of this invention.
Thus, in one broad respect, this invention is a process for the
production of linear alkylbenzenes which comprises contacting
benzene and an olefin having about 8 to about 30 carbons in the
presence of a mixed catalyst bed to form linear alkylbenzenes,
wherein the mixed catalyst bed comprises fluorine-containing
mordenite and a second, solid linear alkylbenzene alkylation
catalyst, wherein the second alkylation catalyst has a selectivity
to the 2-phenyl isomer of the linear alkylbenzenes less than the
selectivity of the fluorine-containing mordenite.
In another broad respect, this invention is a process for the
production of linear alkylbenzenes, comprising: dehydrogenating a
paraffin to form an olefin; sending a feed stream of benzene and
the olefin through a conduit to a linear alkylbenzenes alkylation
reactor containing a fluorine-containing mordenite and a second
alkylation catalyst, wherein the second alkylation catalyst has a
selectivity to the 2-phenyl isomer of the linear alkylbenzenes less
than the selectivity of the fluorine-containing mordenite; reacting
the benzene and olefin in the reactor to form a crude linear
alkylbenzenes stream; distilling the crude linear alkylbenzenes
stream in a first distillation column to separate benzene that did
not react and to form a benzene-free linear alkylbenzenes stream;
distilling the benzene-free linear alkylbenzenes stream in a second
distillation column to separate any paraffin present and to form a
paraffin-free linear alkylbenzenes stream; distilling the
paraffin-free linear alkylbenzene stream in a third distillation
column to provide an overhead of a purified linear alkylbenzene
stream and removing a bottoms stream containing heavies.
This invention, in another broad respect, is a process useful for
the production of monoalkylated benzenes, comprising contacting
benzene with an olefin or a mixture of olefins that contains or
containing from about 8 to about 30 carbons in the presence of
fluorine-containing mordenite under conditions such that linear
monoalkylated benzene is formed.
In a second broad respect, this invention is a process useful for
the production of monoalkylated benzenes, comprising introducing a
feed comprising olefin having about 16 to about 30 carbons and
benzene into a fluorine-containing mordenite catalyst bed under
conditions such that monoalkylated benzene is produced, allowing
benzene, olefin, and monoalkylated benzene to descend (fall) into a
reboiler from the catalyst bed, removing monoalkylated benzene from
the reboiler, and heating the contents of the reboiler such that
benzene refluxes to further contact the fluorine-containing
mordenite.
In another broad aspect, this invention relates to mordenite useful
for alkylating benzene having a silica to alumina molar ratio of
about 10:1 to about 100:1; wherein the mordenite has been treated
with an aqueous hydrogen fluoride solution such that the mordenite
contains from about 0.1 to about 4 percent fluorine by weight.
In another broad respect, this invention is a method useful for the
preparation of fluorine-containing mordenite, comprising contacting
a mordenite having a silica to alumina molar ratio in a range from
about 10:1 to about 100:1 with an aqueous hydrogen fluoride
solution having a concentration of hydrogen fluoride in the range
of from about 0.1 to about 10 percent by weight such that the
mordenite containing fluorine is produced, collecting the
fluorine-containing mordenite by filtration, and drying.
The fluorine treated mordenite catalyst advantageously produces
high selectivities to the 2-phenyl isomer in the preparation of
LAB, generally producing selectivities of about 70 percent or more.
Also, the fluorine treated mordenite enjoys a long lifetime,
preferably experiencing only a 25 percent or less decrease in
activity after 400 hours on stream. A process operated in
accordance with the apparatus depicted in FIGS. 1 and 2 has the
advantage that rising benzene from the reboiler continuously cleans
the catalyst to thereby increase lifetime of the catalyst. In
addition, this invention advantageously produces little or no
dialkylated benzene, which is not particularly as useful for
detergent manufacture, as well as little or no tetralin
derivatives.
Certain terms and phrases have the following meanings as used
herein.
"Meq/g" means milliequivalents of titratable acid per gram of
catalyst, which is a unit used to describe acidity of the
catalysts. Acidity is generally determined by titration with a
base, as by adding excessive base, such as sodium hydroxide, to the
catalyst and then back titrating the catalyst.
"Conv." and "Conversion" mean the mole percentage of a given
reactant converted to product. Generally, olefin conversion is
about 95 percent or more in the practice of this invention.
"Sel." and "Selectivity" mean the mole percentage of a particular
component in the product. Generally, selectivity to the 2-phenyl
isomer is about 70% or more in the practice of this invention.
"LAB" means a mixture linear alkylbenzenes which comprises a
benzene ring appended to any carbon atom of a substantially linear
alkyl chain having any number of carbon atoms in the range of 18 to
30, inclusive. The mordenite catalyst of the present invention is
useful as a catalyst useful in the production of LAB's in
accordance with the process of manufacturing LAB's of this
invention. LAB is useful as starting material to produce sulfonated
LAB, which itself is useful as a surfactant.
"LAB sulfonates" means LAB which has been sulfonated to include an
acidic sulfonate group appended to the benzene ring (thus forming a
"parent acid"), and subsequently rendered to a form more soluble to
aqueous solution than the parent acid by neutralization using any
of alkali metal hydroxides, alkaline earth hydroxides, ammonium
hydroxides, alkylammonium hydroxides, or any chemical agent known
by those skilled in the art to react with linear alkylbenzene
sulfonic acids to form water-soluble LAB sulfonates.
"Detergent range" means an olefin, alkyl group, or molecular
species (including without limitation LAB and LAB sulfonates) that
comprises any number of carbon atoms selected from:16, 17, 18, 19,
20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, as warranted by the
context.
"Substantially linear" when referring to a hydrocarbon or alkyl
chain that is part of an alkylbenzene, whether the alkylbenzene is
sulfonated or not, means a hydrocarbon comprising between 16 and 30
carbon atoms linked to one another to form a straight chain,
wherein the carbon atoms of said straight chain may have only
hydrogen atoms or a methyl group bonded to them as appendages.
"Branched alkyl" when referring to a hydrocarbon or alkyl chain
that is part of an alkylbenzene, whether the alkylbenzene is
sulfonated or not, means a hydrocarbon comprising between 16 and 30
carbon atoms linked to one another to form a straight chain,
wherein one or more of the carbon atoms of said straight chain may
have a hydrogen atom and any alkyl group other than a methyl group
(including without limitation ethyl groups), bonded to them as
appendages.
"Branched alkylbenzene" means a molecular species which comprises a
branched alkyl chain appended to a benzene ring.
"Branched alkylbenzene sulfonate" means a water-soluble salt of a
branched alkylbenzene that has been sulfonated.
"2-phenyl alkylbenzenes" means a benzene ring having at least one
alkyl group attached to it, wherein the alkyl group comprises any
number of carbon atoms between 16 and 30 (including every integral
number therebetween) linked to one another so as to form a
substantially linear chain and wherein the benzene ring is attached
the alkyl group at a carbon atom that is adjacent to the terminal
carbon of the substantially linear chain. Thus, the carbon atom
that is attached to the benzene ring has a methyl group and an
alkyl group attached to it in a 2-phenyl alkylbenzene. Thus, the
2-phenyl isomer of the LAB produced in accordance with this
invention is of the formula: ##STR1##
in which n is from about 13 to about 28 and preferably from about
16 to about 24, and in which R.sub.1, R.sub.2, R.sub.3, R4, and
R.sub.5 are each independently selected from the group consisting
of: hydrogen, methyl, ethyl, propyl, and butyl.
"Sulfonated 2-phenyl alkylbenzenes" means 2-phenyl alkylbenzenes as
defined above which further comprise a sulfonate group attached to
the benzene ring of a 2-phenyl alkylbenzene, regardless of the
position of the sulfonate group on the ring with respect to the
location of the alkyl group. However, it is typical, though not
always the case for the sulfonate group to appear in the position
R.sub.3 above with respect to a single alkyl group attached to the
benzene ring, as shown in the following structure: ##STR2##
"Motor fuel" means those compositions generally recognized by those
in the art as liquid hydrocarbon fuels in the gasoline boiling
range, including hydrocarbon base fuels. Within the meaning of this
term is included those fuels often termed as "petroleum distillate
fuels" by those in the art and which have the above characteristic
boiling points. The term is, however, not intended to be restricted
to straight-run distillate fractions. The distillate fuel can be
straight-run distillate fuel, catalytically or thermally cracked
(including hydrocracked) distillate fuel, or a mixture of
straight-run distillate fuel, naphthas and the like with cracked
distillate stocks. Also, the base fuels used in the formulations of
the fuel compositions of the present invention can be treated in
accordance with well-known commercial methods such as acid or
caustic treatments, hydrogen solvent refining, clay treatment, etc.
Gasolines are supplied in a number of different grades depending
upon the type of service for which they are intended. The gasolines
useful in the present invention include those designed as motor and
aviation gasolines. Motor gasolines include those defined by ASTM
specification D-439-73 and are composed of a mixture of various
types of hydrocarbons including aromatics, olefins, paraffins,
isoparaffins, naphthalenes, and occasionally diolefins. Motor
gasolines normally have a boiling range within the limits of about
20 degrees C. to about 230 degrees C., while aviation gasolines
have narrower boiling ranges, usually within the limits of about 37
degrees C. to 165 degrees C. Also within this definition are the
kerosene range fuels, which include diesel fuels and jet fuel.
"Ashless Dispersants" means any material regarded by those in the
motor fuel arts as possessive of dispersant characteristics and
which upon combustion leaves substantially no ash.
In this specification and the appended claims, all parts and
percentages are expressed in terms of weight percent, unless
specified otherwise.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a representation of a first continuous reactive
distillation column employed in the practice of this invention.
FIG. 2 shows a representation of a second continuous reactive
distillation column employed in the practice of this invention.
FIG. 3 shows a representative process scheme for one embodiment of
this invention where a fluorine-containing mordenite is employed
with a second, solid catalyst to achieve variable 2-phenyl isomer
content depending on the relative proportions of the two
catalysts.
DETAILED DESCRIPTION
The catalysts of this invention are fluorine-containing mordenites,
which is a form of zeolite. A catalyst according to this invention
is prepared from a hydrogen mordenite (typically having 0.1 percent
or less of sodium) having a silica-alumina molar ratio of from
about 10:1 to about 100:1. More typically, the starting mordenite
has a silica/alumina molar ratio of from about 10:1 to about 50:1.
The starting hydrogen mordenite, which is commercially, available,
is treated with an aqueous solution of hydrogen fluoride ("HF") to
produce the active, highly selective catalyst of the invention. In
the course of such HF treatment, as well as during subsequent
calcination of said HF-treated mordenite, the silica/alumina molar
ratio typically increases. Finished catalysts prepared in
accordance with the principles of this invention may have a
fluorine content of from about 0.1 to about 4 percent by weight,
including every hundredth percentage therebetween, but preferably
contain about 1 percent fluorine by weight based upon the total
weight of the finished catalyst.
The aqueous solution used to treat the mordenite may contain a
range of HF concentrations. Generally, the HF concentration is a
minimum of about 0.1 percent by weight. Below such minimum
concentration, the effect of the fluorine treatment significantly
decreases, resulting in the undesirable need for repeated
treatments. However, repeated treatments do ultimately provide a
catalyst material useful according to the invention, and in such
regard these materials are properly considered to be functional
equivalents of other catalysts prepared in accordance with the
invention. Generally, the maximum level of HF in a treating
solution intended to be used for treating a mordenite to provide a
catalyst according to a preferred form of the invention is about 10
percent by weight. Above a concentration of about 10 percent by
weight, the HF-bearing treating solution begins to alter the
crystallinity of the mordenite, and may adversely affect its
catalytic properties.
The aqueous HF solution may be prepared by simple dilution of
commercially available aqueous stock solutions of HF, such as 48%
HF solutions, to a desired concentration. Alternatively, it is
possible to sparge gaseous HF into water to provide an aqueous HF
solution.
Typically, the treatment with aqueous hydrogen fluoride solution is
carried out by adding mordenite powder, pellets, or extrudates to
an aqueous HF solution at a temperature of from about 0.degree. C.
to about 50.degree. C. using agitation and an addition rate
sufficient to prevent lumping of the mordenite, and spattering of
the solution. The agitation of the HF solution to which the
mordenite has been added is continued for a time sufficient to
achieve the desired level of fluorine in the mordenite. This time
may vary, as is known by those skilled in the art, being dependent
on the agitation, temperature, the amount of HF available, which
depends upon the concentration of the HF solution and the relative
amount of HF solution to the amount of mordenite being treated.
After treatment, the mordenite can be recovered by filtration, and
then dried. It is also possible to impregnate the mordenite to
incipient wetness with a given HF solution, as well as to treat the
mordenite with gaseous hydrogen fluoride. Preferably the
fluoride-treated mordenite is calcined in air prior to its being
used in the alkylation process. The preferred calcination
temperature is any degree of temperature in the range from about
400.degree. C. to about 600.degree. C. Mordenite may alternatively
be fluorinated using other materials such as ammonium fluoride,
fluosilicic acid, fluorided silicon compounds, fluorided
hydrocarbons, or any compound capable of losing a fluorine atom to
a mordenite when brought into contact with the mordenite.
The mordenite can be used in the practice of this invention as a
powder, in pellet form, as granules, or as extrudates. The
mordenite may be formed into pellets or extrudates using binders
and techniques well known to those of skill in the art, such as
alumina, silica or mixtures thereof. Catalysts according to the
invention may also be supported on an inert carrier, such as
alumina or silica, as the preparation of supported catalysts is
well known in the art.
Reactants for LAB Production
In the practice of this invention, benzene or a substituted benzene
such as toluene, ethylbenzene, propylbenzene, butylbenzene, or one
or more xylenes is alkylated with an olefinic material to form LAB.
Olefins and benzene can be handled and purified using standard
techniques recognized by those of ordinary skill in the art. In
this regard, it is preferred that the reactants are substantially
free from water and alcohol, as the presence of hydroxy groups
tends to hinder the reaction, possibly by poisoning the catalyst.
The olefins employed in the practice of this invention have from
about 16 to about 30 carbons per molecule, and in one form of the
invention preferably from about 20 to about 24 carbon atoms. It is
most preferred that the olefinic material be a mono-olefin. It is
most preferred that the mono-olefin be an alpha-olefin, in which
the double bond is located in a terminal ethylenic unit.
Commonly, such olefins would be available from a paraffinic media
of the same carbon range. One route by which olefins in the 16 to
30 carbon number range are available is from dehydrogenating a
mixture of paraffins in the same carbon number range, namely
C.sub.-16 to C.sub.-30 paraffins. Such dehydrogenation may be
carried out even if such a paraffin mixture has any appreciable
olefin content, for example, an olefin content in the range of
about 5 to 20%.
Process Conditions, Procedures, and Apparatus
The process of this invention can be carried out using the
continuous reactive distillation column depicted in FIG. 1. In FIG.
1, a feed mixture of benzene and olefin, generally at a
benzene-to-olefin molar ratio range of about 1:1 to 100:1 flows
from feed pump 10 to feed inlet 14 via line 12. The feed mixture
falls to packed mordenite catalyst bed 32 where alkylation in the
presence of the fluorine-containing mordenite occurs.
Alternatively, while not depicted in FIG. 1, the benzene and olefin
can be introduced separately into the bed with mixing occurring in
the bed, or the reactants can be mixed via an in-line mixer prior
to introducing the reactants into the catalyst bed, or the
reactants can be injected separately above the bed with mixing
affected by use of standard packing above the bed, or the reactants
can be sparged into the chamber above the bed. The catalyst bed 32
depicted in FIG. 1 for laboratory scale may be made of two lengths
of 1.1 inch internal diameter tubing, the lengths being 9.5 inches
and 22 inches. In the catalyst bed 32, the falling feed mixture
also contacts rising vapors of unreacted benzene which has been
heated to reflux in reboiler 42 by heater 40. Such rising vapors
pass over thermocouple 38 which monitors temperature to provide
feedback to heater 40. The rising vapors of benzene and/or olefin
also pass through standard packing 36 (e.g., 7.5 inches of goodloe
packing). The rising vapors heat thermocouple 30 which connects to
bottoms temperature controller 28 which activates heater 40 when
temperature drops below a set level.
Prior to startup, the system may be flushed with nitrogen which
enters via line 54 and which flows through line 58. After startup,
a nitrogen blanket is maintained over the system. Also prior to
startup and during nitrogen flush, it may be desirable to heat
catalyst bed 32 so as to drive off water from the
fluorine-containing mordenite.
Residual water from the feed mixture or which otherwise enters the
system is collected in water trap 24 upon being liquefied at
condenser 21 (along with benzene vapor). If the feed is very dry
(free of water) the water trap 24 may not be needed. Removing water
leads to longer catalyst lifetime. Hence, the water trap 24 is
optional. The same applies to FIG. 2. Condenser 21 is cooled via
coolant such as water entering condenser 21 via port 22 and exiting
via port 20. As needed, water in water trap 24 may be drained by
opening drain valve 26.
As needed, when LAB content in reboiler 42 rises to a desired
level, the bottoms LAB product may be removed from the system via
line 47, using either gravity or bottoms pump 48 to withdraw the
product. When product is so withdrawn, valve 44 is opened.
In FIG. 1, dip tube 46, which is optional, is employed to slightly
increase the pressure in reboiler 42 to thereby raise the boiling
point of benzene a degree or two. Likewise, a pressure generator 56
may be optionally employed to raise the pressure of the system.
Other standard pressure increasing devices can be employed.
Pressure can thus be increased in the system such that the boiling
point of benzene increases up to about 200.degree. C.
In FIG. 1, control mechanisms for heat shutoff 50 and pump shutoff
52 are depicted which serve to shut off heat and pump if the
liquids level in the system rises to such levels. These control
mechanisms are optional and may be included so that the catalyst
bed does not come into contact with the bottoms of the
reboiler.
In the practice of this invention in the alkylation of benzene, a
wide variety of process conditions can be employed. In this regard,
the temperature in the catalyst bed may vary depending on
reactants, rate of introduction into the catalyst bed, size of the
bed, and so forth. Generally, the bed is maintained at the reflux
temperature of benzene depending on pressure. Typically, the
temperature of the catalyst bed is above about 70.degree. C., and
most likely about 78.degree. C. or more in order to have reasonable
reaction rates, and about 200.degree. C. or less to avoid
degradation of reactants and products and to avoid deactivation of
the catalyst by coke build-up. Preferably, the temperature is in
the range from about 80.degree. C to about 140.degree. C. The
process may be operated at a variety of pressures during the
contacting step, with pressures of about atmospheric most typically
being employed. When the process is operated using a system as
depicted in FIGS. 1 and 2, the reboiler temperature is maintained
such that benzene and olefin vaporize, the temperature varying
depending on olefin, and generally being from about 80.degree. C.
to about 250.degree. C. for olefins having 10 to 14 carbons. The
composition of the reboiler will vary over time, but is generally
set initially to have a benzene olefin ratio of about 10:1, with
this ratio being maintained during the practice of this invention.
The rate of introduction of feed into the catalyst bed may vary,
and is generally at a liquid hourly space velocity ("LHSV") of
about 0.05 hr.sup.-1 to about 10 hr.sup.-, more typically from
about 0.05 hr.sup.-1 to about 1 hr.sup.-1. The mole ratio of
benzene to olefin introduced into the catalyst bed is generally
from about 1:1 to about 100:1. In commercial benzene alkylation
operations, it is common to run at mole ratios of from about 2:1 to
about 20:1, which can suitably be employed in the practice of this
invention, and to charge said olefins as an olefin-paraffin mixture
comprising 5% to 20% olefin content. Said olefin-paraffin mixtures
are normally generated commercially through dehydrogenation of the
corresponding paraffin starting material over a noble metal
catalyst.
Another continuous reactive distillation apparatus is depicted in
FIG. 2. In FIG. 2, the feed mixture enters the reactor via feed
inlet 114. The feed mixture falls through the column into catalyst
bed 132, wherein alkylation to form LAB occurs. A thermowell 133
monitors the temperature of said catalyst bed 132. The catalyst bed
132 may be optionally heated externally and is contained within
1-1/4 inch stainless steel tubing. Goodloe packing is positioned at
packing 136 and 137. LAB product, as well as unreacted benzene and
olefin, fall through packing 136 into reboiler 142. In reboiler
142, electric heater 140 heats the contents of reboiler 142 such
that heated vapors of benzene and olefin rise from the reboiler 142
to at least reach catalyst bed 132. As needed, the bottoms LAB
product may be removed from reboiler 142 by opening bottoms valve
144 after passing through line 147 and filter 145. Residual water
from the feed mixture, or which otherwise enters the system, may be
condensed at condenser 121 which is cooled with coolant via inlet
line 122 and exit line 120. The condensed water falls ; to water
trap 124, which can be drained as needed by opening drain valve
126. Temperature in the system is monitored via thermocouples 138,
130, and 165. The system includes pressure release valve 166. A
nitrogen blanket over the system is maintained by introduction of
nitrogen gas via inlet line 154. Level control activator 150
activates bottoms level control valve 151 to open when the liquids
level in the reboiler rises to the level control activator 150.
While the systems depicted in FIG. 1 and FIG. 2 show single
catalyst bed systems, it must be appreciated that multi-catalyst
bed reactors are within the scope of this invention, as well as
multiple ports for inlet feeds, water traps, product removal lines,
and so forth. Moreover, the process may be run in batch mode, or in
other continuous processes using plugflow designs, trickle bed
designs, and fluidized bed designs.
As average molecular weight of olefins increases, particularly when
the average number of carbons is greater than about 15, the
selectivity to the 2-isomer is less than for lower molecular weight
olefins. It is thus preferred, although not absolutely necessary,
that the product of the alkylation using HF-treated mordenite is
sent to a second, finishing catalyst bed to improve yield. An
example of such a second catalyst is HF-treated clay such as
montmorillonite clay treated in accordance with the invention to
have about 0.5% fluoride and calcined as stated earlier.
Variable 2-phenyl Isomer Content of Product Using the Mordenite of
this Invention in Combination With a Second, Solid LAB Alkylation
Catalyst
The fluorine-containing mordenite of this invention generally
produces LAB having high 2-phenyl isomer content, such as higher
than about 70%. Conventional LAB alkylation technology does not,
however, achieve these higher 2-phenyl isomer levels. The
conventional LAB catalysts used most frequently are HF alkylation
catalysts and aluminum chloride alkylation catalysts. Other
alkylation catalysts in use today include, various zeolites,
alumina-silica, various clays, as well as other catalysts. The use
of hydrogen fluoride, for instance, produces about 16-18 percent of
the 2-phenyl isomer in the product stream from the reactor. Using
aluminum chloride as a catalyst produces LAB having between about
26-28 percent of the 2-phenyl isomer.
I have found that the mordenite of this invention can be used in
combination with conventional solid LAB alkylation catalysts, such
as silica-alumina (with or without fluorine treatment, such as
disclosed in U.S. Pat. No. 5,196,574), clay and aluminum chloride.
Since conventional LAB alkylation catalysts produce product having
a 2-phenyl isomer content much less than that from the mordenite,
combining the mordenite of this invention and a second solid
alkylation catalyst may be used to achieve an LAB product having a
higher 2-phenyl isomer content than which could be achieved by the
conventional, solid LAB alkylation catalyst alone. In practice, the
2-phenyl isomer content of the final LAB product may be varied by
adjusting the relative amounts of the two catalysts employed and/or
the flow rate of reactants over each catalyst. For a given desired
2-phenyl isomer content of the product, the relative proportions of
the two catalysts may vary depending on activity of each catalyst,
the type and flow rates of the reactants, temperature, pressure,
and other process variables.
FIG. 3 depicts a representative, non-limiting scheme for the
practice of this invention. The catalysts (which may be used as a
mixture or packed in series in the reactor 230, or loaded into two
reactors aligned in series) are employed in amounts effective to
achieve the desired level of 2-phenyl isomer content. If the
catalysts are employed in series, whether in the same reactor or in
multiple reactors, the amount of the first catalyst in the series
is an amount relative to the amount and/or flow rate of the
reactants that is insufficient to effect complete conversion of the
reactants. The second catalyst may be used in any amount which will
complete reaction of the reactants. The fluorine-containing
mordenite may be either the first or second catalyst, preferably
being in the first bed. Alternatively, either bed of catalyst in
reactor 230 may be packed with a single catalyst, or a mixed bed of
the two catalysts.
The scheme of FIG. 3 is shown in the context of LAB alkylation
based on a feed from a paraffin dehydrogenation facility. Thus, in
FIG. 3 fresh paraffin is fed to a conventional dehydrogenation
apparatus 210 via line 211, with recycled paraffin being introduced
from the paraffin column 250 via line 252. Dehydrogenated paraffin
from the dehydrogenation apparatus 210 is then pumped into an
alkylation reactor (or reactors) 230 that contains the
fluorine-containing mordenite and a second, solid alkylation
catalyst. The dehydrogenated paraffin feed may of course be
supplied from any provider. The source of dehydrogenated paraffin
(olefin) is not critical to the practice of this invention. LAB
product from alkylation unit 230 may thereafter be purified by a
series of distillation towers.
In this regard, alkylation effluent may be delivered to a benzene
column 240 by way of line 231. It should be appreciated that the
alkylation product may be sent offsite for purification. Further,
the particular purification scheme used is not critical to the
practice of this invention. The scheme depicted in FIG. 3 is
instead representative of a typical commercial operation. In FIG.
3, unreacted benzene is distilled off from the crude LAB product.
Benzene is then recycled to the alkylation reactor 230. The
benzene-free LAB crude product from the benzene column 240 is
pumped through line 241 to paraffin column 250 where any paraffin
present is distilled off, with the distilled paraffin being
recycled to paraffin dehydrogenation unit 210 via line 252.
Paraffin-free crude LAB from the paraffin column 250 is transported
to a refining column 260 where purified LAB is distilled and
removed via line 262. Heavies (e.g., dialkylates and olefin
derivatives) are withdrawn from refining column 260 via conduit
261.
It should be appreciated that columns 240, 250, and 260 may be
maintained at conditions (e.g., pressure and temperature) well
known to those of skill in the art and may be packed with
conventional materials, if desired.
REPRESENTATIVE EXAMPLES
The following examples are illustrative of the present invention
and are not intended to be construed as limiting the scope of the
invention or the claims. In the examples, all reactants were
commercial grades and used as received. The apparatus depicted in
FIG. 1 was employed for examples 2-4. The apparatus depicted in
FIG. 2 was used for example 5.
It is worthy of note that example 2 illustrates LAB production from
paraffin dehydrogenate using the fluoride-treated mordenite
catalyst of example B, where good catalyst life (250+hrs) is
achieved without catalyst regeneration, while maintaining a
2-phenyl LAB selectivity of >70% and high LAB productivity
without significant loss of fluoride. Comparative example 1, on the
other hand, using untreated mordenite, with no fluoride added,
shows a rapid decline in LAB production.
In addition, examples 3 and 4 illustrate LAB production using a 5:1
molar benzene/C.sub.10 -C.sub.14 olefin feed mix and the
fluoride-treated mordenite catalysts of Example B when operating at
different LHSV's in the range of 0.2-0.4 hr.sup.-1. Catalyst life
may exceed 500 hours.
Example 5 illustrates LAB production with the fluoride-treated
mordenite catalyst here the alkylation is conducted at higher
temperatures and under pressure.
Examples 6-8 illustrate the performance of three HF-treated
mordenite catalysts with different fluoride loading.
Example 9 shows how virtually no alkylation activity is observed
with a highly-fluorinated mordenite.
Example A
Preparation of Fluoride-modified Mordenite
To 30 g of acidified mordenite (LZM-8, SiO.sub.2 /Al.sub.2 O.sub.3
ratio 17; Na.sub.2 O wt % 0.02, surface area 517 m.sup.2 /g,
powder, from Union Carbide Corp.) was added 600 ml of 0.4%
hydrofluoric acid solution, at room temperature. After 5 hours the
solid zeolite was removed by filtration, washed with distilled
water, dried at 120.degree. C. overnight, and calcined at
538.degree.C.
Example B
Preparation of a Hydrogen Fluoride-modified Mordenite
To 500 g of acidified, de-aluminized, mordenite (CBV-20A from PQ
Corp.; SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio 20; Na.sub.2 O, 0.02
wt %; surface area 550 m.sup.2 /g, 1/16" diameter extrudates, that
had been calcined at 538.degree. C., overnight) was added a
solution of 33 ml of 48% HF solution in 1633 ml of distilled water,
the mix was cooled in ice, stirred on a rotary evaporator
overnight, then filtered to recover the extruded solids. The
extrudates were further washed with distilled water, dried in vacuo
at 100.degree. C., and then calcined at 538.degree. C., overnight.
Analyses of the treated mordenite showed a fluorine content of 1.2%
and 0.49 meq/g of acidity.
Example 1
Preparation of Linear Alkylbenzenes Using a Hydrogen
Fluoride-modified Mordenite Catalyst
To a 500 ml flask, fitted with condenser and Dean Stark Trap was
added 100 ml of benzene (reagent grade) plus 10 g of hydrogen
fluoride-modified mordenite zeolite, prepared by the method of
Example A. The mix was refluxed for 15-20 minutes to remove small
amounts of moisture, then a combination of benzene (50 ml) plus
1-dodecene (10 g) was injected into the flask and the solution
allowed to reflux for 3 hours.
Upon cooling, the modified mordenite catalyst was removed by
filtration, the filtrate liquid flashed to remove unreacted
benzene, and the bottoms liquid analyzed by gas chromatography.
Analytical data for this catalyst are summarized in Table 1:
TABLE 1 LINEAR LAB DODECENE LAB ISOMER DISTRIBUTION (%) HEAVIES
(LLAB) (%) CONV. (%) 2-Ph 3-Ph 4-Ph 5-Ph 6-Ph (%) (%) 99.7 79.9
16.6 0.8 1.3 1.3 0.2 95.9
Example 2
Preparation of Linear Alkylbenzenes From Paraffin Dehydrogenate
Using a Hydrogen Fluoride-treated Mordenite Catalyst
In this example, benzene was alkylated with a sample of C.sub.10
-C.sub.14 paraffin dehydrogenate containing about 8.5% C.sub.10
-C.sub.14 olefins. Alkylation was conducted in a process unit as
shown in FIG. 1.
Alkylation was conducted by first charging 500 ml of a
benzene/paraffin dehydrogenate mix (10:1 molar ratio,
benzene/C.sub.10 -C.sub.14 olefin) to the reboiler and 250 cc of
the HF-treated mordenite of example B to the 1.1" i.d. reaction
zone. The mordenite was held in place using Goodloe packing. The
reboiler liquid was then heated to reflux and a benzene plus
C.sub.10 -C.sub.14 paraffin dehydrogenate mix (10:1 molar ratio,
benzene/C.sub.10 -C.sub.14 olefin) continuously introduced into the
unit above the catalyst column at the rate of 100 cc/hr. (LHSV=0.4
hr.sup.-1).
Under steady state, reflux, conditions liquid product was
continuously withdrawn water continuously taken off from the water
trap. The crude liquid product was periodically analyzed by gas
chromatography. The reboiler temperature was typically in the
controlled range of 97-122.degree. C. The column head temperature
variability was 78-83.degree. C. A summary of the analytical
results may be found in Table 2.
After 253 hours of continuous operation, the recovered HF-treated
mordenite catalyst contained 1.1% fluorine, an acidity of 0.29
meq/g and a water content of 0.3%.
TABLE 2 Time on Alkylate 2-Phenyl C.sub.6 H.sub.6 Conc. Stream
(Hrs) Sample Conc. (%) Sel. (%) (%) 0 0 1.4 -- 32.3 2 1 3.4 -- 19.7
4 2 5.8 74.9 16.6 6 3 6.6 75.8 25.2 32 4 7.9 80.7 27.0 56 5 7.8
82.7 27.0 69 6 7.3 81.4 27.4 94 7 6.5 82.0 27.8 118 8 6.0 78.4 27.7
142 9 5.9 81.3 26.9 166 10 5.4 81.5 27.3 207 11 5.3 81.3 26.1 229
12 5.1 81.1 27.4 253 13 4.9 81.4 28.1
Comparative Example 1
Preparation of Linear Alkylbenzenes From Paraffin Dehydrogenate
Using an Untreated Mordenite Catalyst
Following the procedures of Example 9, the alkylation unit was
charged with 250 cc of untreated, calcined, mordenite, (the
starting mordenite of Example B), and the liquid feed comprised
benzene plus C.sub.10 -C.sub.14 paraffin dehydrogenate mix in a
10:1 molar ratio of benzene/C.sub.10 -C.sub.14 recovered mordenite
was analyzed to contain an acidity level of 0.29 meq/g and a water
content of 2.1%. Performance results are summarized in Table 3.
TABLE 3 Time on Alkylate 2-Phenyl C.sub.6 H.sub.6 Conc. Stream
(Hrs) Sample Conc. (%) Sel. (%) (%) 0 0 -- -- 11.2 2 1 6.50 -- 9.9
4 2 7.16 73.2 17.1 6 3 7.09 73.1 26.4 22 4 8.61 73.9 26.6 31 5
10.49 67.4 15.8 46 6 7.39 75.0 27.7 70 7 6.39 75.1 28.5 93 8 6.08
73.6 23.0 144 9 5.21 73.6 15.8 157 10 4.40 73.9 26.2 180 11 3.06
69.6 27.1 204 12 1.32 -- 19.5 228 13 1.32 -- 33.3
Example 3
Preparation of Linear Alkylbenzenes From Paraffin Dehydrogenate
Using a Hydrogen Fluoride-treated Mordenite Catalyst
Following the procedures of Example 2, the alkylation unit was
charged with 250 cc of the HF-treated mordenite of Example B, and
the liquid feed comprised a benzene plus C.sub.10 -C.sub.14
paraffin dehydrogenate mix in a 5:1 molar ratio of benzene/C.sub.10
-C.sub.14 olefin, the reboiler temperature was typically in the
range of 122-188.degree. C., the column head temperature
78-83.degree. C. Performance results are summarized in Table 4.
After 503 hours of continuous operation, the recovered HF-treated
mordenite catalyst showed a fluorine content of 1.0%. There were
0.35 meq/g of acidity, and the water content was 0. 1%.
TABLE 4 Corrected.sup.a Time on Alkylate 2-Phenyl C.sub.6 H.sub.6
Alkylate Stream (Hrs) Sample Conc. (%) Sel. (%) Conc. (%) Conc. (%)
0 0 1.0 -- 8.9 1.1 2 1 3.5 61.8 0.3 3.5 4 2 7.1 72.1 0 7.1 6 3 6.8
76.7 7.2 7.3 34 4 8.4 79.7 14.3 9.8 71 5 7.2 81.8 14.6 8.5 96 6 6.5
80.8 15.5 7.7 119 7 6.3 80.6 15.1 7.4 643 8 6.0 81.0 14.3 7.0 168 9
5.9 80.7 14.4 6.9 239 10 5.0 78.2 8.8 5.5 263 11 5.3 79.2 13.5 6.2
288 12 5.0 79.6 16.5 6.0 311 13 5.4 79.4 4.1 5.6 335 14 5.5 79.2
8.2 6.0 408 15 4.9 79.4 13.1 5.6 432 16 4.7 78.8 14.4 5.5 456 17
4.4 78.5 14.1 5.1 479 18.sup.a 4.7 78.6 2.7.sup.b 4.8 488 19.sup.b
4.9 78.5 2.4.sup.c 5.0 503 20.sup.b 5.1 78.9 0.6.sup.c 5.1 .sup.a
Corrected for benzene in effluent sample. .sup.b Applied pressure
8" H.sub.2 O .sup.c Applied pressure 12" H.sub.2 O
Example 4
Preparation of Linear Alkylbenzenes From Paraffin Dehydrogenate
Using a Hydrogen Fluoride-treated Mordenite Catalyst
Following the procedures of Example 2, alkylation was conducted in
the glassware unit of FIG. 1 complete with catalyst column,
reboiler, condenser and controls. To the reaction zone was charged
500 cc of HF-treated mordenite of Example B. The liquid feed
comprised a benzene plus C.sub.10 -C.sub.14 paraffin dehydrogenate
mix in a 5:1 molar ratio of benzene /C.sub.10 -C.sub.14 olefin. The
feed rate was 100 cc/hr (LHSV:0.2 hr.sup.-1).
Under typical steady state, reflux, conditions, with a reboiler
temperature range of 131-205.degree. C. and a head temperature of
76-83.degree. C. Performance results are summarized in Table 5.
TABLE 5 Pressure Reboiler hours on Alkylate Conc. (%) 2-Phenyl
C.sub.6 H.sub.6 Conc. Corrected.sup.a Alkylated (Inch H.sub.2 O)
Temp./.degree. C. stream Sample (%) Sel. (%) Conc. (%) 12 205 2 1
8.2 74.3 0.5 8.3 12 193 4 2 9.2 75.0 0.4 9.2 12 175 6 3 10.0 74.8
2.3 10.3 12 204 21 4 12.7 78.7 0.3 12.7 12 146 44 5 11.7 81.0 10.4
12.9 12 136 68 6 11.5 81.8 10.0 12.7 12 -- 2-3 days C.sup.b 11.6
81.4 9.4 12.7 12 136 93 7 11.3 82.6 10.8 12.5 12 -- 4-5 days
C-1.sup.b 11.0 81.8 11.0 12.2 12 142 165 8 10.4 83.0 11.4 11.5 12
142 189 9 10.2 83.4 10.5 11.2 12 146 213 10 9.7 80.2 11.2 10.7 12
139 238 11 9.6 83.4 11.1 10.7 12 143 261 12 9.9 81.9 11.0 11.0 12
133 333 13 9.2 83.4 11.3 10.3 12 138 356 14 8.9 83.5 11.1 9.9 12
138 381 15 8.8 83.0 11.3 9.8 12 131 405 16 8.7 82.8 11.2 9.7 .sup.a
Corrected for benzene in effluent sample .sup.b Composite
product
Example 5
Preparation of Linear Alkylbenzenes From Paraffin Dehydrogenate
Using a Hydrogen Fluoride-treated Mordenite Catalyst
Following the procedures of Example 2, alkylation of benzene with
C.sub.10 -C.sub.14 paraffin dehydrogenate was conducted using the
stainless-steel unit of FIG. 2, complete with catalyst column,
reboiler, condenser, and controls. About 250 cc or HF-treated
mordenite of Example B was charged to the column. The liquid feed
comprised benzene plus C.sub.10 -C.sub.- paraffin dehydrogenate mix
in a 10:1 molar ratio of benzene/C.sub.10 -C.sub.14 olefin. The
LHSV varied from 0.2 to 0.4 hr.sup.-1. Alkylation was conducted
over a range of column and reboiler temperatures and a range of
exit pressures. Performance results are summarized in Table 6.
TABLE 6 Pressure Column Temp DIFF EXIT Pot Temp. Time Sample
Alkylate Conc. 2-Phenyl C.sub.6 H.sub.6 (.degree. C.) (psi) (psi)
(.degree. C.) (hr) (#) (%) Sel. (%) Conc. (%) 149-129 0.1 0 188 4 1
3.8 -- 6.3 152-126 0 0 200 20 2 1.8 -- 32.7 195-108 0 0 199 25 3
5.7 -- 8.7 218-111 0 0 201 28 4 0.8 -- 67.5 212-118 0 0 201 44 5
8.8 71.7 4.5 209-114 0.2 0 198 52 6 2.4 -- 47.3 228-116 0 0 197 68
7 6.9 72.6 12.4 187-107 0.5 0 197 76 8 2.9 74.6 44.1 -- -- -- -- 76
9.sup.a 4.8 72.9 25.3 -- -- -- -- -- 9C.sup.b 6.8 72.2 1.0 174-107
0 0 178 6 10 4.1 79.2 54.9 170-106 0 0 172 22 11 2.0 -- 59.8 -- --
-- -- 28 12.sup.a 6.6 76.8 26.8 142-107 0 0 136 31 13 4.8 67.9 18.9
141-110 0 0 138 47 14 4.4 65.9 16.9 142-110 0 0 136 55 15 5.0 63.9
16.6 168-111 0 0 131 71 16 4.1 64.8 16.7 170-108 0 0 150 79 17 5.0
72.0 8.8 175-113 0 0 143 95 18 5.9 68.1 15.2 145-106 0 5.2 188 14
19 3.2 60.2 9.0 149-108 0 4.2 186 20 20 4.8 66.3 12.0 160-118 0
11.7 213 29 21 4.2 -- 6.7 160-119 0 9.3 210 44 22 5.2 -- 6.6 .sup.a
Composite product .sup.b Stripped composite product
Examples 6, 7, 8
Preparation of Linear Alkylbenzenes Using Hydrogen Fluoride
Modified Mordenite Catalysts With Different Fluoride Treatment
Levels
Following the procedures of Example 1, the alkylation unit was
charged with benzene (100 ml), a 10 g sample of hydrogen
fluoride-modified mordenite prepared by the procedure of Example B,
plus a mix of benzene (50 ml) and 1-decene (10 g). Three HF-treated
mordenites were tested, having the composition:
Catalyst "C" 0.25% HF on mordenite (CBV-20A) Catalyst "D" 0.50% HF
on mordenite (CBV-20A) Catalyst "E" 1.0% HF on mordenite
(CBV-20A)
In each experiment samples of the bottoms liquid fraction were
withdrawn at regular periods and subject to gas chromatography
analyses. Performance results are summarized in Table 7.
TABLE 7 CATALYST TIME % LLAB % ISOS % HVY % 2Ph % 3Ph % 4Ph % 5Ph %
6 & 7Ph D 10 11.75 0.14 0 73.36 21.87 2.89 0.94 1.02 20 12.43
0.21 0 72.97 21.96 3.14 1.13 0.81 30 12.88 0.21 0 72.67 22.13 3.03
1.16 1.01 40 12.27 0.22 0 73.02 21.92 2.85 1.06 1.14 50 12.15 0.98
0 72.46 21.67 3.21 1.17 1.49 50 12.24 1.01 0 72.53 21.63 3.23 1.12
1.44 60 12.28 0.21 0 72.96 22.07 2.93 1.14 0.91 60 11.98 0.21 0
72.97 22.21 2.93 1.17 0.83 C 10 12.2 0.18 0 72.54 22.46 3.21 0.98
0.82 20 12.7 0.39 0 71.51 22.61 2.91 1.02 2.13 30 12.52 0.21 0
71.96 22.68 2.96 1.04 1.36 40 12.75 0.21 0 71.84 22.67 3.22 1.02
1.25 50 12.98 0.21 0 71.57 22.81 3.16 1.08 1.39 60 12.54 0.21 0
71.45 22.81 3.19 1.12 1.44 60 12.33 0.21 0 71.61 22.87 2.92 1.05
1.31 E 10 10.56 0.05 0 75.19 19.41 2.18 3.22 20 12.95 0.15 0 74.36
19.23 3.01 3.4 30 13.44 0.18 0 74.11 19.42 3.2 3.27 40 13.16 0.15 0
074.16 19.38 3.12 3.34 50 13.1 0.15 0 74.43 19.16 3.21 3.28 60
12.83 0.15 0 74.28 19.49 2.88 3.35 60 12.87 0.16 0 73.82 19.97 2.8
3.2
Example 9
Illustrating the Inactivity of a Heavily Loaded Hydrogen-fluoride
Modified Mordenite Catalyst
Following the procedures of Example 2, the alkylation unit was 100
cc of a hydrogen floride-treated mordenite (CBV-20A) prepared by
the method of Example B but having a much higher loading of HF
(fluoride content 4.8%). The acidity of said HF-treated mordenite
was 0.15 meq/g. No significant amount of alkylated product was
detected in the reactor effluent by gas chromatography.
Thus, the foregoing examples are illustrative of the preparation of
catalysts and alkylbenzenes according to the invention. In cases
where it is desired to append olefins having carbon numbers in the
range of 18 to 30, the catalysts and reaction conditions and
process procedures are identical to those provided above, with such
well known variables as distillation temperatures being readily
adjusted accordingly to the desires of the operator of ordinary
skill in this art.
Example 10
Preparation of High Molecular Weight Alkylbenzenes Using
Fluoridated Clay
This example illustrates the preparation of high molecular weight
alkylbenzenes in the C.sub.18 to C.sub.24 range using 16.times.30
mesh fluoridated clay catalyst. For this example, the catalyst is
first desired under 30-mmHg vacuum at 120-130.degree. C. for 4
hours prior to use. To a 500 ml round bottom flask fitted with a
condenser, Dean Stark trap, and a thermometer, was added 10 grams
of catalyst and 80 ml of reagent benzene. The contents were
magnetically stirred and heated to benzene reflux. About 25 ml of
azeotrope was removed and 10 grams of C.sub.18 to C.sub.24 olefin
was added while being stirred. The reaction is monitored by GC or
bromine number. The reaction was monitored by taking samples every
one hour and was stopped after three hours. The cooled reaction
mixture was filtered to remove catalyst and benzene was removed by
distillation. The bormine number of colorless alkylate product was
determined to asses the olefin conversion and the product was also
analyzed using gas chromatography. An olefin conversion of 78% was
achieved.
Example 11
Preparation of High Molecular Weight Alkylbenzenes Using
Fluoridated Clay
Another run was carried out in accordance with the procedures
outlined for Example 10 using a feedstock of C.sub.20 -C.sub.24
olefin and fluoridated clay as catalyst. An olefin conversion of
99% was obtained.
Example 12
Preparation of High Molecular Weight Alkylbenzenes Using
Fluoridated Clay
Another run was carried out in accordance with the procedures
outlined for Example 10 using a feedstock of C.sub.24 -C.sub.28
olefin using fluoridated clay as catalyst. An olefin conversion of
82% was achieved with a 2-phenyl isomer content of 30%.
Example 13
Preparation of High Molecular Weight Alkylbenzene
This example illustrates the preparation of high molecular weight
alkylbenzene from a feedstock comprising C.sub.20 -C.sub.24, using
a mordenite catalyst produced in accordance with the invention. The
acidic form of the catalyst from example 4 above was dried and
calcined, and was re-dried as in example 1 prior to using
conditions as in example 12 above. An olefin conversion of 98% was
achieved, with a 74% 2-phenyl isomer content.
Example 14
Preparation of High Molecular Weight Alkylbenzene
One more run was carried out using fluoridated mordenite catalyst
according to example 4 and C.sub.24 -C.sub.28 olefin under
conditions employed in example 12. An olefin conversion of 68% was
achieved, having a 70% 2-phenyl isomer content.
Example 15
Preparation of High Molecular Weight Alkylbenzene
This example illustrates the preparation of C.sub.20 -C.sub.24
alkylate from C.sub.20 -C.sub.24 olefins using hydrogen fluoride
treated mordenite catalyst. In this example, benzene was alkylated
with C.sub.20 -C.sub.24 olefins and the alkylation was conducted in
a process unit as shown in FIG. 1. The reactor was filled with 300
ml of 0.1%-fluoridated mordenite. The catalyst was held in position
by Goodloe packing, and the alkylation was conducted by first
charging 500-ml benzene/paraffin mixture in a 3:1 ratio to the
reboiler. The reboiler charge was heated to reflux, and about 15 ml
of benzene azeotrope was drained from the overhead trap to ensure
anhydrous conditions in the reactor. Overhead Dean-Stark trap
draining was done for every 24 hours. The feed mixture containing
benzene and C.sub.20 -C.sub.24 olefin in 10:1 mole ratio was
introduced continuously above the catalyst bed where feed comes in
contact with refluxing benzene vapors. Benzene azeotrope is
collected into the overhead trap and dry reactants enter into the
catalyst bed to form the alkylate. At steady state a sample is
withdrawn from the reboiler, benzene was removed and analyzed for
olefin conversion by bromine number method and 2-phenyl isomer
content by gas chromatography.
Bromine Time, % Olefin Number Hrs Conversion Comments 23.1 0 0
starting olefin 0.36 68 98.44 Benzene/Olefin ratio of 10 0.31 136
98.67 Overhead drained every 24 hrs. 0.22 304 99.06 0.12 472 99.48
0.18 544 99.2 0.14 592 99.4
Example 16
Preparation of High Molecular Weight Alkylbenzene
In this example, to improve the performance of the reactor and to
prolong the life of the catalyst, draining frequency of the
overhead trap was increased from once every 24 hours to once in
every 8 hours.
Bromine Time, % Olefin Number Hrs Conversion Comments 0.08 736
99.65 Overhead drained every 8 hrs. 0.02 808 99.9 0.26 976 98.9 No
overhead drained during weekend 0.08 1120 99.65 0.19 1192 99.18
Overhead drained once a day
Example 17
Preparation of High Molecular Weight Alkylbenzene
In this example, the benzene olefin ratio of 10 was lowered to 5 to
improve the efficiency of the operation. The draining of overhead
trap was done once in every 8 hours.
Bromine Number Time, Hrs % Olefin Conversion Comments 0.13 1360
99.44 Benzene/Olefin ratio of 5 0.1 1432 99.6 0.21 1504 99.1 0.05
1592 99.78
Hydrocarbon and other base oils such as the vegetable oils are
known to be rarely used in their pure forms in any application, but
rather contain various chemical additives designed to increase the
performance of such oils, or to extend the useful lives of either
the oils themselves or the equipment in which they are designed to
function. In this regard, the prior art teaches the use of various
oil additives which include without limitation:detergents,
dispersants, anti-wear agents, extreme pressure additives,
antioxidants, corrosion inhibitors, viscosity modifiers, pour point
depressants, antifoam agents, friction modifiers, metal
deactivators, water scavengers, free radical scavengers, and
compatibilizers.
Although the present invention has been described largely in
reference to the alkylation of benzene using olefins as an
alkylating agent, it should be appreciated that substituted
benzenes are also useful as starting materials within the context
of the present invention, provided that the chemical groups
appended to the benzene ring are not prohibitively de-activating of
the benzene ring structure. In this regard, toluene is a
functionally equivalent starting material which may be used in
place of all or part of the benzene employed. Other substituted
benzenes such as xylenes are also useful in this regard, as well as
ethylbenzene, propylbenzene, and butylbenzene.
In cases where a substituted benzene is alkylated in accordance
with the principles of this invention, the reaction product
consists predominantly of para-substituted reaction products, with
some ortho substitution. Subsequent sulfonation of such a mixture
to provide sulfonate derivatives results in a mixture of sulfonates
or their salts or esters as well. These materials may be
conveniently described by the formula: ##STR3##
in which n may be any integer between 13 and 27, and in which
R.sub.1, R.sub.2, R.sub.3, R4, and R.sub.5 are each independently
selected from the group consisting of: hydrogen, methyl, ethyl,
propyl, butyl, sulfonic acid, sulfonate, and salts and esters
thereof.
Detergents Useful in Hydrocarbon Oils
One popular class of detergents used in lubricating oils, cutting
fluids, and the like are the oil soluble sulfonates. Within this
broad class are the aromatic sulfonates of the type described in
this specification, particularly the LAB sulfonates. These
materials are preferred because of their effectiveness and
compatibility with other components found in finished oil products,
their widespread availability, and relatively low cost.
Additionally, many of these detergent materials are anionic in
nature, which means that any one of a wide range of selected
cationic species may accompany the anionic detergent, which is of
particular benefit when it is desired to incorporate other metals
into the composition. The most commonly used salts of these acids
in hydrocarbon oils are the sodium, potassium, lithium, calcium,
magnesium, strontium and barium salts. The "basic salts" are those
metal salts known to the art wherein the metal is present in a
stoichiometrically larger amount than that necessary to neutralize
the acid. The calcium- and barium-overbased petrosulfonic acids are
typical examples of such basic salts.
The terms "overbased," "superbased," and "hyperbased," are terms of
art which are generic to well known classes of the metallic
sulfonates and other materials. These overbased materials have also
been referred to as "complexes," "metal complexes," "high-metal
containing salts," and the like. Overbased materials are
characterized by a metal content in excess of that which would be
present according to the stoichiometry of the metal and the
particular organic compound reacted with the metal, e.g., a
sulfonic acid. Thus, if a monosulfonic acid such as an LAB
sulfonate is neutralized with a basic metal compound, e.g., calcium
hydroxide, the "normal" metal salt produced will contain one
equivalent of calcium for each equivalent of acid. However, as is
well known in the art, various processes are available which result
in an inert organic liquid solution of a product containing more
than the stoichiometric amount of metal. The solutions of these
products are referred to herein as overbased materials. Following
these procedures, the sulfonic acid or an alkali or alkaline earth
metal salt thereof can be reacted with a metal base and the product
will contain an amount of metal in excess of that necessary to
neutralize the acid, for example, 4.5 times as much metal as
present in the normal salt or a metal excess of 3.5 equivalents.
The actual stoichiometric excess of metal can vary considerably,
for example, from about 0.1 equivalent to about 30 or more
equivalents depending on the reactions, the process conditions, and
the like. These overbased materials useful in preparing the
disperse systems will contain from about 3.5 to about 30 or more
equivalents of metal for each equivalent of material which is
overbased. In the present specification and claims the term
"overbased" is used to designate materials containing a
stoichiometric excess of metal and is, therefore, inclusive of
those materials which have been referred to in the art as
overbased, superbased, hyperbased, etc., as discussed supra.
The overbased materials are prepared by treating a reaction mixture
comprising the organic material to be overbased, a reaction medium
consisting essentially of at least one inert, organic solvent for
said organic material, a stoichiometric excess of a metal base, and
a promoter with an acidic material. The methods for preparing the
overbased materials as well as an extremely diverse group of
overbased materials are well known in the prior art and are
disclosed for example in the following U.S. Pat. Nos.: 2,616,904;
2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049;
2,695,910, 2,723,234; 2,723,235; 2,723,236; 2,760,970; 2,767,164;
2,767,209; 2,777,874; 2,798,852; 2,839,470; 2,856,359; 2,859,360;
2,856,361; 2,861,951; 2,883,340; 2,915,517; 2,959,551; 2,968,642;
2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581; 3,108,960;
3,147,232; 3,133,019; 3,146,201; 3,152,991; 3,155,616; 3,170,880;
3,170,881; 3,172,855; 3,194,823; 3,223,630; 3,232,883; 3,242,079;
3,242,080; 3,250,710; 3,256,186; 3,274,135; 3,492,231; and
4,230,586. These patents disclose processes, materials which can be
overbased, suitable metal bases, promoters, and acidic materials,
as well as a variety of specific overbased products useful in
producing the disperse systems of this invention and are,
accordingly, incorporated herein by reference. Other detergents
known to those skilled in the art are useful as a component of a
composition according to the invention in addition to the LAB based
detergents described herein.
Dispersants Useful in Hydrocarbon Oils
Although a dispersant used in a hydrocarbon oil may be a
multifunctional material that can confer other beneficial
properties to a base oil, dispersants are primarily used in
hydrocarbon oils for their ability to maintain small particles of
dirt, combustion products, metal fines, etc. in the liquid phase,
to prevent deposition and accumulation of sludges in places where
eddy currents exist in various equipment and wares.
The use of acylated nitrogen compounds as dispersants in lubricants
is disclosed in numerous patents, including U.S. Pat. Nos.
3,172,892; 3,219,666; 3,272,746; 3,310,492; 3,341,542; 3,444,170;
3,455,831; 3,455,832; 3,576,743; 3,630,904; 3,632,511; 3,804,763;
and 4,234,435.
The book "Lubricant Additives" by M. W. Ranney, published by Noyes
Data Corporation of Parkridge, N.J. (1973), discloses a number of
overbased metal salts of various sulfonic acids which are useful as
detergent/dispersant in lubricants. The book also entitled
"lubricant Additives" by C. V. Smallheer and R. K. Smith, published
by the Lezius-Hiles Co. of Cleveland, Ohio (1967), similarly
discloses a number of overbased sulfonates which are useful as
dispersants. U.S. Pat. No. 4,100,082 discloses the use of neutral
or overbased metal salts of organic sulfur acids as
detergent/dispersants for use in fuels and lubricants.
Ashless detergents and dispersants are so called despite the fact
that, depending on its constitution, the dispersant may upon
combustion yield a non-volatile material such as boric oxide or
phosphorus pentoxide; however, it does not ordinarily contain metal
and therefore does not yield a metal-containing ash on combustion.
Many types are known in the art, and any of them are suitable for
use in the lubricant compositions and functional fluids of this
invention. The following are illustrative of dispersants, not
delimitive of the term, and are incorporated by reference herein:
(1) Reaction products of carboxylic acids (or derivatives thereof)
containing at least about 34 and preferably at least about 54
carbon atoms with nitrogen containing compounds such as amine,
organic hydroxy compounds such as phenols and alcohols, and/or
basic inorganic materials. Examples of these "carboxylic
dispersants" are described in many U.S. Pat. Nos., including
3,219,666; 4,234,435; and 4,938,881. These include the products
formed by the reaction of a polyisobutenyl succinic anhydride with
an amine such as a polyethylene amine. (2) Reaction products of
relatively high molecular weight aliphatic or alicyclic halides
with amines, preferably oxyalkylene polyamines. These may be
characterized as "amine dispersants" and examples thereof are
described for example, in the following U.S. Pat. Nos.:3,275,554;
3,438,757; 3,454,555; and 3,565,804. (3) Reaction products of alkyl
phenols in which the alkyl group contains at least about 30 carbon
atoms with aldehydes (especially formaldehyde) and amines
(especially polyalkylene polyamines), which may be characterized as
"Mannich dispersants." The materials described in the following
U.S. Pat. Nos. are illustrative: 3,649,229; 3,697,574; 3,725,277;
3,725,480; 3,726,882; and 3,980,569. (4) Products obtained by
post-treating the amine or Mannich dispersants with such reagents
as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocarbon-substituted succinic anhydrides, nitriles,
epoxides, boron compounds, phosphorus compounds or the like.
Exemplary materials of this kind are described in the following
U.S. Pat. Nos. 3,639,242; 3,649,229; 3,649,659; 3,658,836;
3,697,574; 3,702,757; 3,703,536; 3,704,308; and 3,708,422. (5)
Interpolymers of oil-solubilizing monomers such as decyl
methacrylate, vinyl decyl ether and high molecular weight olefins
with monomers containing polar substituents, e.g., aminoalkyl
acrylates or acrylamides and poly-(oxyethylene)-substituted
acrylates. These may be characterized as "polymeric dispersants"
and examples thereof are disclosed in the following U.S. Pat. Nos.
3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; and
3,702,300.
Antiwear Agents
A composition according to this invention may also include a
sulfur-, phosphorus-, or sulfur- and phosphorus-containing antiwear
agent. The term antiwear agent is used to refer to compounds which
provide wear protection properties to lubricating compositions and
functional fluids. Antiwear agents are useful in controlling wear
and may sometimes also act as extreme pressure agents and as
antioxidants. These antiwear agents include sulfurized organic
compounds, hydrocarbyl phosphates, phosphorus-containing amides,
phosphorus-containing carboxylic esters, phosphorus-containing
ethers, and dithiocarbamate-containing compounds. Examples of
hydrocarbyl phosphates include hydrocarbyl thiophosphates.
Thiophosphates may contain from one to about three sulfur atoms,
preferably one or two sulfur atoms. Thiophosphates are prepared by
reacting one or more phosphites with a sulfurizing agent including
sulfur, sulfur halides, and sulfur containing compounds. Salts of
thiophosphates include zinc dithiophosphates. Other antiwear agents
known to those skilled in the art are useful as a component of a
composition according to the invention. Other dispersants known to
those skilled in the art are useful as a component of a composition
according to the invention.
Anti-oxidants
A particularly valuable class of additives known as antioxidants
are widely used in lubricating oil formulations, cutting oils, and
functional fluids. Antioxidants are materials which inhibit
oxidative decomposition of the oil under consideration. Although
several examples are given below, these examples should be
considered exemplary only of the wide variety of antioxidants which
may be usefully combined with the detergent components of this
invention.
In U.S. Pat. No. 2,282,710 to Dietrich issued May 12, 1942 it is
known that stabilization of petroleum hydrocarbons against the
deleterious catalytic action of metals may be obtained by
compositions containing both a nitrogen and a sulfur functional
group. Various cyclic, aromatic and linear carbon configurations
are shown in the sulfur and nitrogen containing molecules of
Dietrich. Dietrich discloses preparing his compositions by the use
of ethyleneimine. Dietrich further states that his compounds are
particularly effective in retarding the formation of products
corrosive to metals, and particularly cadmium, silver, copper, lead
and like bearing alloys under normal service conditions.
German OLS 1,066,019 published Sep. 24, 1959 by Holtschmitt et al
describes various condensation products of thioglycol and nitrogen
containing materials. Holtschmitt shows his compounds as containing
free hydroxyl groups. Holtschmitt further discloses the use of
aromatic amines containing a short aliphatic group on the aromatic
ring, e.g. toluidine.
It is known from an article entitled Thioglycol Polymers 1
Hydrochloric Acid-Catalysed Auto Condensation of Thiodiglycol by
Woodward, Journal of Polymer Science the OL XLI, Pages 219-223
(1959), that the properties of a sulfur and oxygen containing
compound allow end-to-end condensation. It is further known from
the Woodward article that multiple sulfur linkages within the
molecule, e.g. disulfides, trisulfides, and the like may be
obtained.
It is further known that various amines may be utilized in
antioxidant compositions. Phenothiazine compounds are known in
lubricant products from U.S. Pat. No. 2,781,318 issued Feb. 12,
1957 to Cyphers. The alkyl phenothiazines of Cyphers are alkylated
on the phenylene rings of the phenothiazine structure. Cyphers does
not show or suggest the alkylation of the amine nitrogen in
phenothiazine. The Cyphers patent is directed to the utility of
phenothiazine as an antioxidant and corrosion inhibiting additive
for ester, polyester, polyether and other synthetic lubricants.
U.S. Pat. No. 3,536,706 issued Oct. 27, 1970 to Randell suggests
that phenothiazines may be used as additives for synthetic
lubricants. The phenothiazines particularly described by Randell
are those containing tertiary alkyl substituents having from 4 to
12 carbon atoms on the aryl groups which make up the phenothiazine
structure. Randell also discloses fused rings on the two phenylene
groups which make up the phenothiazine structure. Stated otherwise,
Randell allows the utilization of naphthalene for at least one of
the two aryl groups in the phenothiazine structure. U.S. Pat. No.
3,803,140 issued to Cook et al on Apr. 9, 1974 describes various
tertiary alkyl derivatives of phenothiazine. N-alkyl substitution
or N-alkenyl substitution is described on the phenothiazine
structure. Ring alkylation when the phenothiazine is in the free
nitrogen form is also shown. Cook et al express a preference for
non-N substituted phenothiazine derivatives.
Cook et al also suggest that organic materials which are
susceptible to oxidative degradation may benefit through the use of
the compounds of their invention. Such uses include antioxidants
for aliphatic hydrocarbons such as gasoline, lubricating oils,
lubricating greases, mineral oils, waxes, natural and synthetic
polymers such as rubber, vinyl, vinylidene, ethers, esters, amides
and urethanes. The compounds of Cook et al are also suggested for
stabilizing aldehydes and unsaturated fatty acids or esters
thereof. Still further utilities suggested by Cook et al include
the stabilization of organo-metalloid substances such as silicone
polymers. Another class of uses of the compounds of Cook et al
include the stabilization of vitamins, essential oils, ketones and
ethers.
Normant in U.S. Pat. No. 3,560,531 issued Feb. 2, 1971, describes
metallation of materials having active hydrogens including
phenothiazine. U.S. Pat. No. 3,344,068 issued Sep. 26, 1967, to
Waight et al describes antioxidants for ester-based lubricants.
Waight et al's compounds have an N-hydrocarbyl substituted
phenothiazine structure. The N-substituted phenothiazine compounds
of Waight et al are also substituted in at least one position on
the fused aromatic nuclei. A second required component in the
compositions of Waight et al is a secondary aromatic amine having
two aromatic groups attached to the nitrogen atom.
The preparation of alkylthioalkanols which are useful as
intermediates for preparing the compounds of the present invention
are described in U.S. Pat. No. 4,031,023 to Musser et al. The
Musser et al patent was issued Jun. 21, 1977 and is assigned to The
Lubrizol Corporation.
U.S. Pat. No. 2,194,527 to Winthrop et al which issued Nov. 24,
1959, describes pharmaceutical compounds such as
omega-(10-phenothiazinyl)alkyl di-alkyl sulfonium salts which are
useful as spasmolytics and in particular antihistaminics. U.S. Pat.
No. 3,376,224 issued Apr. 2, 1968 to Elliott et al describes
phenothiazine derivatives which are stated to be N-substituted
methylene compounds which contain an ether linkage between the
methylene group and an alkyl or cycloalkyl radical. According to
Elliott et al, the alkyl or cycloalkyl radical may carry an alkoxy
or other non-reactive substituent.
U.S. Pat. No. 4,915,858 describes a composition of matter which is
the amine terminated reaction product obtained from two equivalents
of a secondary aromatic monoamine with at least two equivalents of
a betathiodialkanol. Other antioxidants known to those skilled in
the art are useful as a component of a composition according to the
invention.
Corrosion Inhibitors
Corrosion-inhibiting agents are exemplified by chlorinated
aliphatic hydrocarbons such as chlorinated wax; organic sulfides
and polysulfides such as benzyl disulfide, bis(chlorobenzyl)
disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic
acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized
terpene; phosphosulfurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl oleate;
phosphorus esters including principally dihydrocarbon and
trihydrocarbon phosphites such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite,
dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl phosphite,
diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such
as zinc dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate; Group II metal phosphorodithioates such as zinc
dioctylphosphorodithioate, zinc dicyclohexylphosphorodithioate,
barium di(heptylphenyl)phosphorodithioate, cadmium
dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic
acid produced by the reaction of phosphorus pentasulfide with an
equimolar mixture of isopropyl alcohol and n-hexyl alcohol. Other
corrosion inhibitors known to those skilled in the art are useful
as a component of a composition according to the invention.
Viscosity Modifiers
Viscosity modifiers generally are polymeric materials characterized
as being hydrocarbon-based polymers generally having number average
molecular weights between about 25,000 and 500,000 more often
between about 50,000 and 200,000. Such materials are typically
added to a hydrocarbon based oil and the oil is heated, with
agitation, until the polymeric material is dissolved.
Polyisobutylene has been used as a viscosity modifier in
lubricating oils. Polymethacrylates (PMA) are prepared from
mixtures of methacrylate monomers having different alkyl groups.
Most PMA's are viscosity-modifiers as well as pour point
depressants. The alkyl groups may be either straight chain or
branched chain groups containing from 1 to about 18 carbon
atoms.
Ethylene-propylene copolymers, generally referred to as OCP can be
prepared by copolymerizing ethylene and propylene, generally in a
solvent, using known catalysts such as a Ziegler-Natta initiator.
The ratio of ethylene to propylene in the polymer influences the
oil-solubility, oil-thickening ability, low temperature viscosity,
pour point depressant capability and engine performance of the
product. The common range of ethylene content is 45-60% by weight
and typically is from 50% to about 55% by weight. Some commercial
OCP's are terpolymers of ethylene, propylene and a small amount of
nonconjugated diene such as 1,4-hexadiene. In the rubber industry,
such terpolymers are referred to as EPDM (ethylene propylene diene
monomer). The use of OCP's as viscosity modifiers in lubricating
oils has increased rapidly since about 1970, and the OCP's are
currently one of the most widely used viscosity modifiers for motor
oils.
Esters obtained by copolymerizing styrene and maleic anhydride in
the presence of a free radical initiator and thereafter esterifying
the copolymer with a mixture of C.sub.4-18 alcohols also are useful
as viscosity modifying additives in motor oils. The styrene esters
generally are considered to be multifunctional premium viscosity
modifiers. The styrene esters in addition to their viscosity
modifying properties also are pour point depressants and exhibit
dispersancy properties when the esterification is terminated before
its completion leaving some unreacted anhydride or carboxylic acid
groups. These acid groups can then be converted to imides by
reaction with a primary amine.
Hydrogenated styrene-conjugated diene copolymers are another class
of commercially available viscosity modifiers for motor oils.
Examples of styrenes include styrene, alpha-methyl styrene,
ortho-methyl styrene, meta-methyl styrene, para-methyl styrene,
para-tertiary butyl styrene, etc. Preferably the conjugated diene
contains from four to six carbon atoms. Examples of conjugated
dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene,
isoprene and 1,3-butadiene, with isoprene and butadiene being
particularly preferred. Mixtures of such conjugated dienes are
useful.
The styrene content of these copolymers is in the range of about
20% to about 70% by weight, preferably about 40% to about 60% by
weight. The aliphatic conjugated diene content of these copolymers
is in the range of about 30% to about 80% by weight, preferably
about 40% to about 60% by weight.
These copolymers typically have number average molecular weights in
the range of about 30,000 to about 500,000, preferably about 50,000
to about 200,000. The weight average molecular weight for these
copolymers is generally in the range of about 50,000 to about
500,000, preferably about 50,000 to about 300,000.
The above described hydrogenated copolymers have been described in
the prior art such as in U.S. Pat. Nos. 3,551,336; 3,598,738;
3,554,911; 3,607,749; 3,687,849; and 4,181,618 which are hereby
incorporated by reference for their disclosures of polymers and
copolymers useful as viscosity modifiers in oil compositions
according to this invention. For example, U.S. Pat. No. 3,554,911
describes a hydrogenated random butadiene-styrene copolymer, its
preparation and hydrogenation. The disclosure of this patent is
incorporated herein by reference. Hydrogenated styrene-butadiene
copolymers useful as viscosity modifiers in the lubricating oil
compositions of the present invention are available commercially
from, for example, BASF under the general trade designation
"Glissoviscal". A particular example is a hydrogenated
styrene-butadiene copolymer available under the designation
Glissoviscal 5260 which has a molecular weight, determined by gel
permeation chromatography, of about 120,000. Hydrogenated
styrene-isoprene copolymers useful as viscosity modifiers are
available from, for example, The Shell Chemical Company under the
general trade designation "Shellvis". Shellvis 40 from Shell
Chemical Company is identified as a diblock copolymer of styrene
and isoprene having a number average molecular weight of about
155,000, a styrene content of about 19 mole percent and an isoprene
content of about 81 mole percent. Shellvis 50 is available from
Shell Chemical Company and is identified as a diblock copolymer of
styrene and isoprene having a number average molecular weight of
about 100,000, a styrene content of about 28 mole percent and an
isoprene content of about 72 mole percent. Other viscosity
modifiers known to those skilled in the art are useful as a
component of a composition according to the invention.
Pour Point Depressants
Pour point depressants may also be included in a formulation
according to the invention. They are a particularly useful type of
additive often included in the lubricating oils and functional
fluids such as cutting oils or other lubricants, and often comprise
oil-soluble polymers. Examples of pour point depressants include
those on page 8 of "Lubricant Additives" by C. V. Smalheer and R.
Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio,
1967, which book is incorporated in its entirety herein by
reference thereto). Other pour point depressants known to those
skilled in the art are useful as a component of a composition
according to the invention.
Antifoam Agents
Anti-foam agents may be used to reduce or prevent the formation of
stable foam and include silicones or organic polymers. Examples of
these and additional anti-foam compositions are described in "Foam
Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976),
pages 125-162, which book is incorporated in its entirety herein by
reference thereto. Other antifoam agents known to those skilled in
the art are useful as a component of a composition according to the
invention.
Friction Modifiers
The oil compositions of the present invention also may contain at
least one friction modifier to provide the lubricating oil with the
proper frictional characteristics for a given application. Various
amines, particularly tertiary amines are effective friction
modifiers. Examples of tertiary amine friction modifiers include
N-fatty alkyl-N,N-diethanol amines, N-fatty alkyl-N,N-diethoxy
ethanol amines, etc. Such tertiary amines can be prepared by
reacting a fatty alkyl amine with an appropriate number of moles of
ethylene oxide. Tertiary amines derived from naturally occurring
substances such as coconut oil and oleoamine are available from
Armour Chemical Company under the trade designation "Ethomeen".
Particular examples are the Ethomeen-C and the Ethomeen-O series.
Sulfur-containing compounds such as sulfurized C.sub. 12-24 fats,
alkyl sulfides and polysulfides wherein the alkyl groups contain
from 1 to 8 carbon atoms, and sulfurized polyolefins also may
function as friction modifiers in the lubricating oil compositions
of the invention. Other friction modifiers known to those skilled
in the art are useful as a component of a composition according to
the invention.
Base Oils
The present invention is broad with respect to the selection of
base oil component used in its blending. Typically, compositions
according to the invention comprise a base oil as a major component
of the composition. For purposes of this specification and the
appended claims the term "base oil" as used herein is intended to
include those materials which are recognized as possessing
lubricity characteristics by those of ordinary skill in the art.
Such materials include, without limitation, materials falling
within the following classes: 1) lubricity agents such as synthetic
polymers (e.g., polyisobutene having a number average molecular
weight in the range of about 750 to about 15,000, as measured by
vapor phase osmometry or gel permeation chromatography); 2) the
polyol ethers (e.g., poly(oxyethylene-oxypropylene)ethers); 3)
ester oils including natural and synthetic triglycerides; 4)
natural oil fractions such as mineral oils and those referred to as
bright stocks (including all relatively viscous products formed
during conventional lubricating oil manufacture from petroleum).
Thus, any oil or other material recognized by those skilled in the
art as possessing lubricity characteristics may be used as a base
oil for purposes of this invention.
Ashless Dispersants
Within the prior art in the realm of motor fuel are a wide range of
materials regarded as ashless dispersants by those of ordinary
skill in such art. There are a great l0 many materials capable of
functioning in this regard, including various Mannich bases,
ethyleneamines, polylakylene polyamines, and other primary,
secondary and tertiary amines known in the art. The following is
provided to be exemplary and not delimitive of the scope of ashless
dispersants which may be employed in the context of the present
invention.
A large number of such ashless dispersants are derivatives of high
molecular weight carboxylic acid acylating agents. Typically, the
acylating agents are prepared by reacting an olefin (e.g., a
polyalkene such as polybutene) or a derivative thereof, containing
for example at least about 10 aliphatic carbon atoms or generally
at least 30 to 50 aliphatic carbon atoms, with an unsaturated
carboxylic acid or derivative thereof such as acrylic acid,
methylacrylate, maleic acid, fumaric acid and maleic anhydride.
Dispersants are prepared from the high molecular weight carboxylic
acid acylating agents by reaction with, for example, amines
characterized by the presence within their structure of at least
one N--H group, alcohols, reactive metal or reactive metal
compounds, and combinations of the above. The prior art relative to
the preparation of such carboxylic acid derivatives is summarized
in U.S. Pat. No. 4,234,435.
It also has been suggested that the carboxylic acid derivative
compositions such as those described above can be post-treated with
various reagents to modify and improve the properties of the
compositions. Acylated nitrogen compositions prepared by reacting
the acylating reagents described above with an amine can be
post-treated, for example, by contacting the acylated nitrogen
compositions thus formed with one or more post-treating reagents
selected from the group consisting of boron oxide, boron oxide
hydrate, boron halides, boron acids, esters of boron acid, carbon
disulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic
acid acylating agents, aldehydes, ketones, phosphoric acid,
epoxides, etc. Lists of the prior art relating to post-treatment of
carboxylic ester and amine dispersants with reagents such as those
described above are contained in a variety of patents such as U.S.
Pat. No. 4,203,855 (Col. 19, lines 16-34) and U.S. Pat. No.
4,234,435 (Col. 42, lines 33-46). The use of isophthalic and
terephthalic acids as corrosion-inhibitors is described in U.S.
Pat. No. 2,809,160. The corrosion-inhibitors are used in
combination with detergent additives.
The preparation of lubricating oils containing ashless dispersants
obtained by reaction of aliphatic and aromatic polycarboxylic acids
with acylated amines have been described previously. For example,
U.S. Pat. No. 4,234,435 describes lubricating oils containing
carboxylic acid derivative compositions prepared by post-treating
acylated amines with a variety of compositions including carboxylic
acid acylating agents such as terephthalic acid and maleic acid.
U.S. Pat. No. 3,287,271 and French Pat. No. 1,367,939 describe
detergent-corrosion inhibitors for lubricating oils prepared by
combining a polyamine with a high molecular weight succinic
anhydride and thereafter contacting the resulting product with an
aromatic dicarboxylic acid of from 8 to 14 carbon atoms wherein the
carboxyl groups are bonded to annular carbon atoms separated by at
least one annular carbon atom. Illustrative of such aromatic
dicarboxylic acids are isophthalic acid, terephthalic acid and
various derivatives thereof. Lubricating compositions containing
amine salts of a phthalic acid are described in U.S. Pat. No.
2,900,339. The amine salts are thermally unstable salts of the
phthalic acid and a basic tertiary amine. U.S. Pat. No. 3,692,681
describes dispersions of phthalic acid in hydrocarbon media
containing highly hindered acylated alkylene polyamines. The
polyamines are prepared by reaction of an alkenyl succinic
anhydride with an alkylene polyamine such as ethylene polyamine or
propylene polyamine. The terephthalic acid or its derivative is
dissolved in an auxiliary solvent such as a tertiary alcohol or
DMSO, and a terephthalic acid solution is combined with a
hydrocarbon solution containing the hindered acylated amine address
detergent. The auxiliary solvent then is removed.
U.S. Pat. No. 3,216,936 describes lubricant additives which are
compositions derived from the acylation of alkylene polyamines.
More specifically, the compositions are obtained by reaction of an
alkylene amine with an acidic mixture consisting of a
hydrocarbon-substituted succinic acid having at least about 50
aliphatic carbon atoms in the hydrocarbon group and an aliphatic
monocarboxylic acid, and thereafter removing the water formed by
the reaction. The ratio of equivalents of said succinic acid to the
mono-carboxylic acid in the acidic mixture is from about 1:0.1 to
about 1:1. The aliphatic mono-carboxylic acids contemplated for use
include saturated and unsaturated acids such as acetic acid,
dodecanoic acid, oleic acid, naphthenic acid, formic acid, etc.
Acids having 12 or more aliphatic carbon atoms, particularly
stearic acid and oleic acid, are especially useful. The products
described in the '936 patent also are useful in oil-fuel mixtures
for two-cycle internal combustion engines.
British Pat. No. 1,162,436 describes ashless dispersants useful in
lubricating compositions and fuels. The compositions are prepared
by reacting certain specified alkenyl substituted succinimides or
succinic amides with a hydrocarbon-substituted succinic acid or
anhydride. The arithmatic mean of the chain lengths of the two
hydrocarbon substituents is greater than 50 carbon atoms.
Formamides of monoalkenyl succinimides are described in U.S. Pat.
No. 3,185,704. The formamides are reported to be useful as
additives in lubricating oils and fuels.
U.S. Pat. Nos. 3,639,242 and 3,708,522 describe compositions
prepared by post-treating mono- and polycarboxylic acid esters with
mono- or polycarboxylic acid acylating agents. The compositions
thus obtained are reported to be useful as dispersants in
lubricants and fuels.
One preferred method for preparing compositions according to the
invention is to begin with a major amount of a base oil material
and add the other selected ingredients to the base oil, with
sufficient agitation to provide a homogeneous mixture within a
reasonable time. When the viscosity of the additive is much greater
than that of the base oil, it is beneficial to provide heating to
the base oil to facilitate dissolution and homogeneity. This is
especially true in the cases where polymeric materials are added to
base oils. However, the dissolution of all of the additives used in
the invention in a base oil is well known in the art and is thus
within the skill level of an ordinary artisan in the oil additives
field.
The compositions of the present invention may vary widely in
composition depending upon the intended use of the final
composition. However, those of ordinary skill in formulating
lubricating oils, functional fluids, cutting oils, emulsions, etc.,
in which LAB based detergent materials are used as a component
readily recognize that the detergents prepared from LAB materials
provided by the invention may be used as direct, drop-in
substitutes for many detergent components in current formulations,
including those which are based on linear alkylbenzenes and those
which are not. Compositions which include detergents based upon the
linear alkylbenzenes of the invention offer superior detergency
over formulations which contain linear alkylbenzene based detergent
materials of the prior art, on a molar basis, owing to the unique
isomer distribution provided by the present invention.
Another aspect of the present invention is the use of the LAB
surfactants in fuel formulations on which various internal
combustion engines including diesel, automobile, and jet engines
may be operated. Since the LAB surfactants of this invention may be
anionic in nature, such as in the cases when the detergent molecule
is a sulfonate, it is possible to provide charge balance using a
cation which is known to impart beneficial properties to motor
fuels. Such cations may include the alkali and alkaline earth
metals as the use of such are well known for the properties they
impart to fuel compositions. Further, the prior art discloses many
ashless dispersants useful as additives in fuels and lubricant
compositions. Many of these are cationic in nature and are thus
capable of providing charge balance to chemical compounds in which
the anionic portion is derived from the LAB according to this
invention, to provide a neutral, oil or fuel soluble material which
possesses both detergent and dispersant characteristics.
One particular and surprising advantage of using the catalysts of
this invention to produce alkylbenzenes having relatively high
2-phenyl isomer content is that a low content of dialkylbenzene
components are found in the alkylbenzene product mixture. This is
important since dialkylbenzenes are generally regarded as
undesirable, and the presence of such species tends to raise the
viscosity of the alkylbenzene reaction product mixture. Thus, using
conventional alkylation technology known in the art, it is common
for alkylbenzenes produced in accordance with prior art methods to
have a viscosity greater than about 145 SUS viscosity units at a
temperature of 37.8 degrees centigrade. However, alkylation of
benzene with olefins in the C.sub.16 -C.sub.30 range in accordance
with this invention provides a product having an SUS viscosity of
85 at 37.8 degrees centigrade. Generally speaking, alkylbenzenes
made by alkylation of benzene with olefins in the C.sub.16
-C.sub.30 range using catalysts an procedures taught herein results
in the alkylbenzenes containing less than 1% of
dialkylbenzenes.
Consideration must be given to the fact that although the instant
invention has been shown and described with respect to certain
preferred embodiments including selection of linear alkylbenzenes
from which detergents are produced, it is likely that this
specification shall inspire those skilled in the lubricating arts
upon its reading to make alterations and modifications to
compositions according to the invention and arrive at compositions
substantially equivalent in function. The scope of the present
invention includes all such equivalent alterations and
modifications, and is limited only by the scope of the claims
appended hereto.
* * * * *